start-ver=1.4 cd-journal=joma no-vol=484 cd-vols= no-issue= article-no= start-page=394 end-page=401 dt-received= dt-revised= dt-accepted= dt-pub-year=2018 dt-pub=20180925 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Syntheses and crystal structures of neodymium(III) and europium(III) complexes bearing dimethyl-, pyrrolidine-, or S-prolinol- dithiocarbamato ligands and their natural and magnetic circular dichroism spectra en-subtitle= kn-subtitle= en-abstract= kn-abstract= A series of Nd-III and Eu-III complexes containing achiral or chiral dithiocarbamato (dtc) ligands, [Ln(Xdtc)(3)(NN)] {Ln = Nd or Eu; X = dimethyl- (Me-2), pyrrolidine- (pyr), or (S)-prolinol- (S-proOH); NN = 1,10-phenanthroline (phen) or 2,2'-bipyridine (bpy)}, were prepared and their crystal structures and spectroscopic properties, in particular the natural circular dichroism (CD) and magnetic circular dichroism (MCD), were investigated. The crystal structures of the complexes analyzed by the X-ray diffraction method showed an 8-coordinate geometry around the Ln III center with comparable structural parameters to one another and to the related complexes reported previously. These complexes exhibited similar spectral patterns in their absorption, natural CD and MCD spectra in solution. Weak but characteristic sharp f-f transition bands were observed in the absorption and MCD spectra, but no CD signals associated with these transitions were observed even in the S-proOHdtc complexes. The MCD spectral pattern of the Eu-III complexes revealed a local C-2v symmetry around the Ln(III) center in solution, in contrast to the aqua and the analogous beta-diketonato Eu-III complexes. en-copyright= kn-copyright= en-aut-name=YakubuAbdallah en-aut-sei=Yakubu en-aut-mei=Abdallah kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=SuzukiTakayoshi en-aut-sei=Suzuki en-aut-mei=Takayoshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=KitaMasakazu en-aut-sei=Kita en-aut-mei=Masakazu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Faculty of Education, Okayama University kn-affil= en-keyword=Dithiocarbamate kn-keyword=Dithiocarbamate en-keyword=Lanthanoid kn-keyword=Lanthanoid en-keyword=Crystal structures kn-keyword=Crystal structures en-keyword=Magnetic circular dichroism kn-keyword=Magnetic circular dichroism en-keyword=(S)-prolinol dithiocarbamate kn-keyword=(S)-prolinol dithiocarbamate END start-ver=1.4 cd-journal=joma no-vol=171 cd-vols= no-issue= article-no= start-page=515 end-page=522 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20190812 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Homodinuclear lanthanoid(III) dithiocarbamato complexes bridged by 2,2′-bipyrimidine: Syntheses, structures and spectroscopic properties en-subtitle= kn-subtitle= en-abstract= kn-abstract= Four new homodinuclear lanthanoid(III) dithiocarbamato (RR'dtc(-)) complexes bridged by 2,2'-bipyrimidine (bpm) of the form [{Ln(RR'dtc)(3)}(2)(mu-bpm)] {Ln = Nd or Eu; RR' = dimethyl- (Me-2) or pyrrolidine(pyr)} were prepared and their crystal structures and spectroscopic properties were characterized. The crystallographic studies revealed that all of the complexes possess a similar structural motif with an 8:8-coordination geometry, in which the bpm ligand bridges two Ln(III) centers in the kappa N-2(1,1') : kappa N-2(3,3') mode and three RR'dtc(-) ligands coordinate to each Ln(III) center. The complexes exhibit weak but relatively sharp f-f transition bands in the absorption and magnetic circular dichroism (MCD) spectra recorded in the visible region. The MCD spectral studies demonstrated the magneto-optical behavior of the complexes. The spectral features of the dithiocarbamato complexes were distinctly different from those of their beta-diketonato analogues, suggesting the coordination environment around the Ln(III) center influences the electronic structure and spectroscopic symmetry of the complexes in solution. en-copyright= kn-copyright= en-aut-name=YakubuAbdallah en-aut-sei=Yakubu en-aut-mei=Abdallah kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=SuzukiTakayoshi en-aut-sei=Suzuki en-aut-mei=Takayoshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=KitaMasakazu en-aut-sei=Kita en-aut-mei=Masakazu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=3 en-affil=Faculty of Education, Okayama University kn-affil= en-keyword=2,2 '-Bipyrimidine kn-keyword=2,2 '-Bipyrimidine en-keyword=Dithiocarbamate kn-keyword=Dithiocarbamate en-keyword=Homodinuclear kn-keyword=Homodinuclear en-keyword=Electronic structure kn-keyword=Electronic structure en-keyword=Magnetic circular dichroism kn-keyword=Magnetic circular dichroism END start-ver=1.4 cd-journal=joma no-vol=498 cd-vols= no-issue= article-no= start-page=119124 end-page= dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20191201 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Dinuclear lanthanoid(III) dithiocarbamato complexes bridged by (E)-N-benzylidenepicolinohydrazonate: Syntheses, crystal structures and spectroscopic properties en-subtitle= kn-subtitle= en-abstract= kn-abstract= (E)-N-Benzylidenepicolinohydrazide (Hbphz) was used to synthesize a series of hydrazonato-bridged homodinuclear Ln(2)(III) dithiocarbamato (RR'dtc(-)) complexes of the form [{Ln(RR' dtc)(2)}(2)(mu-bphz)(2)] {Ln= La, Pr, Nd, Sm or Eu; RR'= dimethyl-(Me-2) or pyrrolidine-(pyr)}. X-ray crystallographic studies revealed that these complexes possessed a common head-to-tail type dinuclear structural motif in which two hydrazonato ligands bridged two Ln(III) centers in the mu- 1 kappa N-2(py),O:2 kappa O-2,N(imine) mode and two RR'dtc ligands coordinated to each Ln(III) center. Interestingly, while the Sm-III and Eu-III complexes crystallized as simple 8:8-coordinate dinuclear molecules, the lighter Ln(III) (i.e. La-III, Pr-III and Nd-III) complexes afforded in some cases 9:9-coordinate molecules, where the ninth coordination site was occupied by a solvent ethanol or methanol molecule. Even for the lighter Ln(III) complexes, the complexes were solved in dichloromethane or chloroform as the 8:8-coordinate dimer, as revealed by H-1 NMR spectroscopy. In the UV-visible absorption and magnetic circular dichroism (MCD) spectra of the complexes, similar spectral patterns for ligand-centered and Laporte forbidden f-f transitions were observed. The MCD spectral studies demonstrated the characteristic magneto-optical behavior of the complexes. en-copyright= kn-copyright= en-aut-name=YakubuAbdallah en-aut-sei=Yakubu en-aut-mei=Abdallah kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=SuzukiTakayoshi en-aut-sei=Suzuki en-aut-mei=Takayoshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=KitaMasakazu en-aut-sei=Kita en-aut-mei=Masakazu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=3 en-affil=Faculty of Education, Okayama University kn-affil= en-keyword=Hydrazone kn-keyword=Hydrazone en-keyword=Dithiocarbamate kn-keyword=Dithiocarbamate en-keyword=Crystal structures kn-keyword=Crystal structures en-keyword=Lanthanoid kn-keyword=Lanthanoid en-keyword=Magnetic circular dichroism kn-keyword=Magnetic circular dichroism END start-ver=1.4 cd-journal=joma no-vol=22 cd-vols= no-issue=3 article-no= start-page=458 end-page=466 dt-received= dt-revised= dt-accepted= dt-pub-year=2019 dt-pub=20191206 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Transition-metal(ii) complexes with a tripodal hexadentate ligand, 1,1,1-tris[2-aza-3-(imidazol-4-yl)prop-2-enyl]ethane, exhibiting incomplete total or absolute spontaneous resolution en-subtitle= kn-subtitle= en-abstract= kn-abstract=Crystal structures and crystallisation behaviours of a series of first-row transition-metal(II) complexes bearing 1,1,1-tris[2-aza-3-(imidazol-4-yl)prop-2-enyl]ethane (H3L), [MII(H3L)]Cl(ClO4) (M = Mn, Fe, Co, Ni and Zn) were examined. These compounds crystallise in an orthorhombic crystal system with a non-enantiogenic (Sohncke) space group P212121, resulting in spontaneous resolution of the chiral complex cations. Hydrogen bonds between the imidazole N–H atoms in the tripodal ligand and chloride anions give enantiomorphic crystals with a homochiral three-dimensional network structure. In order to verify the spontaneous resolution of these compounds, solid-state circular dichroism spectra of the resulting single crystals were measured (KBr disk method). Unexpectedly, the observed spectra indicated that imbalanced formation of the enantiomorphic crystals (i.e., left-handed Λ-form vs. right-handed Δ-form complex cations) in all cases. Moreover, in the cases of NiII and ZnII compounds, predominant enantiomorphic crystals formed by spontaneous resolution were always the same (in at least ten of our recrystallisation experiments). These observations suggest that there is a certain (but as yet unknown) factor that affects the predominant deposition of either enantiomorphic crystal when spontaneous resolution takes place from a solution of a racemic mixture in which rapid racemisation occurs. en-copyright= kn-copyright= en-aut-name=MatsushimaMisaki en-aut-sei=Matsushima en-aut-mei=Misaki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=WadaKoki en-aut-sei=Wada en-aut-mei=Koki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=TakaharaKazuma en-aut-sei=Takahara en-aut-mei=Kazuma kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=SunatsukiYukinari en-aut-sei=Sunatsuki en-aut-mei=Yukinari kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=SuzukiTakayoshi en-aut-sei=Suzuki en-aut-mei=Takayoshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=5 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=E76 cd-vols= no-issue= article-no= start-page=1813 end-page=1817 dt-received= dt-revised= dt-accepted= dt-pub-year=2020 dt-pub=2020 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Comparison of mol­ecular structures of cis-bis­[8-(di­methyl­phosphan­yl)quinoline]­nickel(II) and -platinum(II) complex cations en-subtitle= kn-subtitle= en-abstract= kn-abstract=The crystal structures of the complexes (SP-4-2)-cis-bis[8-(dimethylphosphanyl)quinoline-κ2 N,P]nickel(II) bis(perchlorate) nitromethane monosolvate, [Ni(C11H12NP)2](ClO4)2·CH3NO2 (1), and (SP-4-2)-cis-bis[8-(dimethylphosphanyl)quinoline-κ2 N,P]platinum(II) bis(tetrafluoroborate) acetonitrile monosolvate, [Pt(C11H12NP)2](BF4)2·C2H3N (2), are reported. In both complex cations, two phosphanylquinolines act as bidentate P,N-donating chelate ligands and form the mutually cis configuration in the square-planar coordination geometry. The strong trans influence of the dimethylphosphanyl donor group is confirmed by the Ni—N bond lengths in 1, 1.970 (2) and 1.982 (2) Å and, the Pt—N bond lengths of 2, 2.123 (4) and 2.132 (4) Å, which are relatively long as compared to those in the analogous 8-(diphenylphosphanyl)quinoline complexes. Mutually cis-positioned quinoline donor groups would give a severe steric hindrance between their ortho-H atoms. In order to reduce such a steric congestion, the NiII complex in 1 shows a tetrahedral distortion of the coordination geometry, as parameterized by τ4 = 0.199 (1)°, while the PtII complex in 2 exhibits a typical square-planar coordination geometry [τ4 = 0.014 (1)°] with a large bending deformation of the ideally planar Me2Pqn chelate planes. In the crystal structure of 2, three F atoms of one of the BF4 − anions are disordered over two sets of positions with refined occupancies of 0.573 (10) and 0.427 (10). en-copyright= kn-copyright= en-aut-name=MoriMasatoshi en-aut-sei=Mori en-aut-mei=Masatoshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=SuzukiTakayoshi en-aut-sei=Suzuki en-aut-mei=Takayoshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= en-keyword=8-quinolylphosphane kn-keyword=8-quinolylphosphane en-keyword=asymmetrical bidentate ligand kn-keyword=asymmetrical bidentate ligand en-keyword=square-planar coordination kn-keyword=square-planar coordination en-keyword=tetra­hedral distortion kn-keyword=tetra­hedral distortion en-keyword=trans influence kn-keyword=trans influence en-keyword=trans influence kn-keyword=trans influence END start-ver=1.4 cd-journal=joma no-vol=179 cd-vols= no-issue= article-no= start-page=114401 end-page= dt-received= dt-revised= dt-accepted= dt-pub-year=2020 dt-pub=20200315 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=A specific formation of an iridium(III) hydrido complex bearing 8-(diphenylphosphino)quinoline en-subtitle= kn-subtitle= en-abstract= kn-abstract=A reaction of [Cp*IrCl(Ph2Pqn)]PF6 {Cp* = η5-pentamethylcyclopentadienyl; Ph2Pqn = 8-(diphenylphosphino)quinoline} and Ag(CF3SO3) in methanol afforded orange crystals of the corresponding hydrido complex, [Cp*IrH(Ph2Pqn)]PF6, which was identified by 1H, 31P{1H} NMR and IR spectroscopy as well as X-ray structural analysis. The reactions in deuterated solvents indicated that formation of the hydrido complex proceeded via β-hydrogen elimination of the coordinated methanol molecule. It was also revealed that the hydrido formation was specific for the complex bearing Ph2Pqn ancillary ligand; the analogous complex with 1,2-bis(diphenylphosphino)benzene (diphos) or 1,10-phenanthroline (phen) did not give the corresponding hydrido complex by a similar reaction with Ag+ in methanol. In order to elucidate the reason for the different reactivity among these complexes, the crystal structures of the precursor chlorido complexes, [Cp*IrCl(Ph2Pqn)]PF6, [Cp*IrCl(diphos)]PF6 and [Cp*IrCl(phen)]PF6, as well as an acetonitrile complex of [Cp*Ir(Ph2Pqn)(CH3CN)](PF6)2, were also determined by X-ray analysis. The resulting structural information suggested that a specific formation of the hydrido complex with Ph2Pqn could be originated from the facile formation of the corresponding methanol complex and the hemilabile nature of ancillary Ph2Pqn ligand, which induced the reactivity of the coordinated methanol toward β-hydrogen elimination. en-copyright= kn-copyright= en-aut-name=AriyoshiKeita en-aut-sei=Ariyoshi en-aut-mei=Keita kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=KoteraMai en-aut-sei=Kotera en-aut-mei=Mai kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=NamiokaAtsushi en-aut-sei=Namioka en-aut-mei=Atsushi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=SuzukiTakayoshi en-aut-sei=Suzuki en-aut-mei=Takayoshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= affil-num=1 en-affil=Department of Chemistry, Faculty of Science, Okayama University kn-affil= affil-num=2 en-affil=Department of Chemistry, Faculty of Science, Osaka University kn-affil= affil-num=3 en-affil=Department of Chemistry, Faculty of Science, Okayama University kn-affil= affil-num=4 en-affil=Department of Chemistry, Faculty of Science, Okayama University kn-affil= en-keyword=8-Quinolylphosphine kn-keyword=8-Quinolylphosphine en-keyword=Hydrido complex kn-keyword=Hydrido complex en-keyword=Ancillary ligand effect kn-keyword=Ancillary ligand effect en-keyword=β-Hydrogen elimination kn-keyword=β-Hydrogen elimination en-keyword=Methanol complex kn-keyword=Methanol complex END start-ver=1.4 cd-journal=joma no-vol=405 cd-vols= no-issue= article-no= start-page=112905 end-page= dt-received= dt-revised= dt-accepted= dt-pub-year=2021 dt-pub=20210115 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Exploring reaction pathways for the structural rearrangements of the Mn cluster induced by water binding in the S3 state of the oxygen evolving complex of photosystem II en-subtitle= kn-subtitle= en-abstract= kn-abstract=Photosynthetic oxidation of water to dioxygen is catalyzed by the Mn4CaO5 cluster in the protein-cofactor complex photosystem II. The light-driven catalytic cycle consists of four observable intermediates (S0, S1, S2, and S3) and one transient S4 state. Recently, using X-ray free-electron laser crystallography, two experimental groups independently observed incorporation of one additional oxygen into the cluster during the S2 to S3 transition, which is likely to represent a substrate. The present study implicates two competing reaction routes encountered during the structural rearrangement of the catalyst induced by the water binding and immediately preceding the formation of final stable forms in the S3 state. This mutually exclusive competition involves concerted versus stepwise conformational changes between two isomers, called open and closed cubane structures, which have different consequences on the immediate product in the S3 state. The concerted pathway involves a one-step conversion between two isomeric hydroxo forms without changes to the metal oxidation and total spin (Stotal = 3) states. Alternatively, in the stepwise process, the bound waters are oxidized and transformed into an oxyl–oxo form in a higher spin (Stotal = 6) state. Here, density functional calculations are used to characterize all relevant intermediates and transition structures and demonstrate that the stepwise pathway to the substrate activation is substantially favored over the concerted one, as evidenced by comparison of the activation barriers (11.1 and 20.9 kcal mol−1, respectively). Only after formation of the oxyl–oxo precursor can the hydroxo species be generated; this occurs with a slow kinetics and an activation barrier of 17.8 kcal mol−1. The overall thermodynamic driving force is likely to be controlled by the movements of two glutamate ligands, D1-Glu189 and CP43-Glu354, in the active site and ranges from very weak (+0.4 kcal mol−1) to very strong (–23.5 kcal mol−1). en-copyright= kn-copyright= en-aut-name=IsobeHiroshi en-aut-sei=Isobe en-aut-mei=Hiroshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=ShojiMitsuo en-aut-sei=Shoji en-aut-mei=Mitsuo kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=SuzukiTakayoshi en-aut-sei=Suzuki en-aut-mei=Takayoshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=ShenJian-Ren en-aut-sei=Shen en-aut-mei=Jian-Ren kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=YamaguchiKizashi en-aut-sei=Yamaguchi en-aut-mei=Kizashi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= affil-num=1 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=2 en-affil=Center for Computational Science, University of Tsukuba kn-affil= affil-num=3 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=4 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=5 en-affil=Institute for NanoScience Design, Osaka University kn-affil= en-keyword=Photosynthesis kn-keyword=Photosynthesis en-keyword=Water oxidation kn-keyword=Water oxidation en-keyword=Photosystem II kn-keyword=Photosystem II en-keyword=Oxygen evolving complex kn-keyword=Oxygen evolving complex en-keyword=Mn4CaO6 cluster kn-keyword=Mn4CaO6 cluster en-keyword=Ligand environment kn-keyword=Ligand environment END start-ver=1.4 cd-journal=joma no-vol=27 cd-vols= no-issue=20 article-no= start-page=6788 end-page= dt-received= dt-revised= dt-accepted= dt-pub-year=2022 dt-pub=20221011 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Selective Formation of Unsymmetric Multidentate Azine-Based Ligands in Nickel(II) Complexes en-subtitle= kn-subtitle= en-abstract= kn-abstract=A mixture of 2-pyridine carboxaldehyde, 4-formylimidazole (or 2-methyl-4-formylimidazole), and NiCl2 center dot 6H(2)O in a molar ratio of 2:2:1 was reacted with two equivalents of hydrazine monohydrate in methanol, followed by the addition of aqueous NH4PF6 solution, afforded a Ni-II complex with two unsymmetric azine-based ligands, [Ni(HLH)(2)](PF6)(2) (1) or [Ni(HLMe)(2)](PF6)(2) (2), in a high yield, where HLH denotes 2-pyridylmethylidenehydrazono-(4-imidazolyl)methane and HLMe is its 2-methyl-4-imidazolyl derivative. The spectroscopic measurements and elemental analysis confirmed the phase purity of the bulk products, and the single-crystal X-ray analysis revealed the molecular and crystal structures of the Ni-II complexes bearing an unsymmetric HLH or HLMe azines in a tridentate kappa(3) N, N', N" coordination mode. The HLH complex with a methanol solvent, 1 center dot MeOH, crystallizes in the orthorhombic non-centrosymmetric space group P2(1)2(1)2(1) with Z = 4, affording conglomerate crystals, while the HLMe complex, 2 center dot H2O center dot Et2O, crystallizes in the monoclinic and centrosymmetric space group P2(1)/n with Z = 4. In the crystal of 2 center dot H2O center dot Et2O, there is intermolecular hydrogen-bonding interaction between the imidazole N-H and the neighboring uncoordinated azine-N atom, forming a one-dimensional polymeric structure, but there is no obvious magnetic interaction among the intra- and interchain paramagnetic Ni-II ions. en-copyright= kn-copyright= en-aut-name=HayiborKennedy Mawunya en-aut-sei=Hayibor en-aut-mei=Kennedy Mawunya kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=SunatsukiYukinari en-aut-sei=Sunatsuki en-aut-mei=Yukinari kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=SuzukiTakayoshi en-aut-sei=Suzuki en-aut-mei=Takayoshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Advanced Science Research Center, Okayama University kn-affil= affil-num=3 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= en-keyword=(pyridyl)(imidazolyl)azines kn-keyword=(pyridyl)(imidazolyl)azines en-keyword=aldazines kn-keyword=aldazines en-keyword=kryptoracemate kn-keyword=kryptoracemate en-keyword=crystal structure kn-keyword=crystal structure END start-ver=1.4 cd-journal=joma no-vol=26 cd-vols= no-issue=7 article-no= start-page=1004 end-page=1014 dt-received= dt-revised= dt-accepted= dt-pub-year=2024 dt-pub=2024 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=The effect of solvent molecules on crystallisation of heterotrinuclear MII–TbIII–MII complexes with tripodal nonadentate ligands en-subtitle= kn-subtitle= en-abstract= kn-abstract=The crystal structures and crystallisation behaviours of MII–TbIII–MII heterotrinuclear complexes, [(L)MTbM(L)]NO3 (M = Mn and Zn; L3− stands for a conjugated base of H3L = 1,1,1-tris[(3-methoxysalicylideneamino)methyl]ethane), obtained from various organic solvents (MeOH, EtOH, CH2Cl2 and CHCl3) were investigated. The trinuclear complex cation has two asymmetric centres (Δ or Λ) at two MII sites as a result of the twisted tripodal arms of L3−. Single-crystal X-ray diffraction analysis revealed that all the analysed Zn–Tb–Zn complexes had homochiral structures (Δ,Δ- or Λ,Λ-enantiomers) in each single crystal; however, the type of crystallisation behaviour showed clear differences depending on the type of solvent molecule. Specifically, crystallisation from MeOH or CH2Cl2 resulted in the exclusive formation of the Λ-conglomerates with the Λ,Λ-enantiomers—a phenomenon we recently termed ‘absolute spontaneous resolution’. The analogous Mn–Tb–Mn complex crystallised from MeOH also resulted in the same phenomenon as that of Zn–Tb–Zn. In contrast, the meso-type (Δ,Λ) achiral isomer of the Mn–Tb–Mn complex was deposited for the first time in a series of MII–LnIII–MII trinuclear complexes from a CH2Cl2 or EtOH solution. Density functional theory calculations were performed to compare the thermodynamic stability of homochiral (Λ,Λ) and meso-type (Δ,Λ) complex cations of [(L)MnTbMn(L)]+ in MeOH and EtOH. Results were consistent with the molecular structures observed in the crystallographic analysis of the compounds deposited from these solvents. en-copyright= kn-copyright= en-aut-name=TakaharaKazuma en-aut-sei=Takahara en-aut-mei=Kazuma kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=HorinoYuki en-aut-sei=Horino en-aut-mei=Yuki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=WadaKoki en-aut-sei=Wada en-aut-mei=Koki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= en-aut-name=SakataHiromu en-aut-sei=Sakata en-aut-mei=Hiromu kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=4 ORCID= en-aut-name=TomitaDaichi en-aut-sei=Tomita en-aut-mei=Daichi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=5 ORCID= en-aut-name=SunatsukiYukinari en-aut-sei=Sunatsuki en-aut-mei=Yukinari kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=6 ORCID= en-aut-name=IsobeHiroshi en-aut-sei=Isobe en-aut-mei=Hiroshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=7 ORCID= en-aut-name=KojimaMasaaki en-aut-sei=Kojima en-aut-mei=Masaaki kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=8 ORCID= en-aut-name=SuzukiTakayoshi en-aut-sei=Suzuki en-aut-mei=Takayoshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=9 ORCID= affil-num=1 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=2 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=3 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=4 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=5 en-affil=Faculty of Science, Okayama University kn-affil= affil-num=6 en-affil=Advanced Science Research Center, Okayama University kn-affil= affil-num=7 en-affil=Research Institute for Interdisciplinary Science, Okayama University kn-affil= affil-num=8 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= affil-num=9 en-affil=Graduate School of Natural Science and Technology, Okayama University kn-affil= END start-ver=1.4 cd-journal=joma no-vol=564 cd-vols= no-issue= article-no= start-page=121937 end-page= dt-received= dt-revised= dt-accepted= dt-pub-year=2024 dt-pub=20240501 dt-online= en-article= kn-article= en-subject= kn-subject= en-title= kn-title=Synthesis and characterization of iron(II) complex with unsymmetrical heterocyclic (2-pyridyl)(4-imidazolyl)azine en-subtitle= kn-subtitle= en-abstract= kn-abstract=A new iron(II) complex bearing unsymmetrical azine, [Fe(HLH)2](PF6)2·H2O·MeCN (HLH = 2-pyridylmethylidenehydrazono(4-imidazolyl)methane), was synthesized exclusively by a reaction of 2-pyridine carboxaldehyde, 1H-imidazole-4-carboxaldehyde, hydrazine monohydrate and FeCl2·4H2O (in a molar ratio of 2:2:2:1) in methanol, followed by the addition of an aqueous NH4PF6 solution. It was characterized using spectroscopic techniques, elemental analysis, magnetic measurement, and cyclic voltammetry. The molecular and crystal structure of the compound was revealed by X-ray analysis, where an iron(II) ion was surrounded by two HLH azines with a planar E(py),Z(im) conformation, and tridentate κ3N,N’,N” coordination mode, forming a monomeric six-coordinated and diamagnetic complex. The complex cations were linked by water molecules via intermolecular hydrogen-bonding interactions between the imidazole N−H and the neighboring uncoordinated azine-N atom, forming a 1D chain structure. The selective formation of this unsymmetrical azine (HLH) from a stoichiometric mixture of the components would result from the steric preference of the five- and six-membered chelate rings by the 2-pyridyl and 4-imidazolyl azine moieties, respectively, with the E(py),Z(im) configuration. en-copyright= kn-copyright= en-aut-name=HayiborKennedy Mawunya en-aut-sei=Hayibor en-aut-mei=Kennedy Mawunya kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=1 ORCID= en-aut-name=SunatsukiYukinari en-aut-sei=Sunatsuki en-aut-mei=Yukinari kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=2 ORCID= en-aut-name=SuzukiTakayoshi en-aut-sei=Suzuki en-aut-mei=Takayoshi kn-aut-name= kn-aut-sei= kn-aut-mei= aut-affil-num=3 ORCID= affil-num=1 en-affil= kn-affil= affil-num=2 en-affil= kn-affil= affil-num=3 en-affil= kn-affil= en-keyword=(Pyridyl)(imidazolyl)azine kn-keyword=(Pyridyl)(imidazolyl)azine en-keyword=Aldazines kn-keyword=Aldazines en-keyword=Iron(II) complex kn-keyword=Iron(II) complex en-keyword=Crystal structure kn-keyword=Crystal structure END