Faculty Profiles - SUNATSUKI Yukinari

Papers - SUNATSUKI Yukinari

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Intramolecular [π4s + π4s] photocycloaddition of carbon- and nitrogen-bridged [32](1,4)naphthalenophanes Reviewed

Yukiko Oguma, Masanori Yamamoto, Yukinari Sunatsuki, Hiromi Ota, Minoru Yamaji, Hideki Okamoto

Photochemical & Photobiological Sciences 23 ( 8 ) 1509 - 1519 2024.7

Language：English Publishing type：Research paper (scientific journal) Publisher：Springer Science and Business Media LLC

Abstract

[3₂](1,4)Naphthalenophanes, bearing carbon-bridge chains (syn- and anti-NPs) and nitrogen-bridge chains (syn- and anti-ANPs), were synthesized, and their X-ray structures and photoreactions were investigated. The intramolecular separation distance between the naphthalene cores for ANPs was shorter than that for NPs, suggesting that intramolecular interactions between the naphthalene rings were more efficient for ANPs compared to NPs. Upon photoirradiation at 300 nm, anti-NP, syn-ANP and anti-ANP produced the corresponding intramolecular [π4s + π4s] cycloadducts, whereas syn-NP gave an unidentified complex product mixture. Quantum yields for the photo-consumption (Φ_PC) of NPs and ANPs were evaluated to quantitatively compare their photoreactivity. The Φ_PC values of ANPs were approximately two-fold higher than those of ANPs.Noteworthily, the Φ_PC value of syn-ANP was estimated to be unity. Based on these results we discuss the effects of the alignments of the naphthalene cores (antivs. syn) and the bridging elements (C-bridge vs. N-bridge) on the photoreaction efficiencies of [3₂](1,4)naphthalenophanes.

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DOI： 10.1007/s43630-024-00610-w

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Other Link： https://link.springer.com/article/10.1007/s43630-024-00610-w/fulltext.html

Synthesis and characterization of iron(II) complex with unsymmetrical heterocyclic (2-pyridyl)(4-imidazolyl)azine Reviewed

Kennedy Mawunya Hayibor, Yukinari Sunatsuki, Takayoshi Suzuki

Inorganica Chimica Acta 564 121937 - 121937 2024.5

Development of a novel AAK1 inhibitor via Kinobeads-based screening Reviewed

Akari Yoshida, Satomi Ohtsuka, Fumiya Matsumoto, Tomoyuki Miyagawa, Rei Okino, Yumeya Ikeda, Natsume Tada, Akira Gotoh, Masaki Magari, Naoya Hatano, Ryo Morishita, Ayano Satoh, Yukinari Sunatsuki, Ulf J. Nilsson, Teruhiko Ishikawa, Hiroshi Tokumitsu

Scientific Reports 14 ( 1 ) 6723 2024.3

Language：English Publishing type：Research paper (scientific journal) Publisher：Springer Science and Business Media LLC

Abstract

A chemical proteomics approach using Ca²⁺/calmodulin-dependent protein kinase kinase (CaMKK) inhibitor–immobilized sepharose (TIM-063-Kinobeads) identified main targets such as CaMKKα/1 and β/2, and potential off-target kinases, including AP2-associated protein kinase 1 (AAK1), as TIM-063 interactants. Because TIM-063 interacted with the AAK1 catalytic domain and inhibited its enzymatic activity moderately (IC₅₀ = 8.51 µM), we attempted to identify potential AAK1 inhibitors from TIM-063-derivatives and found a novel AAK1 inhibitor, TIM-098a (11-amino-2-hydroxy-7H-benzo[de]benzo[4,5]imidazo[2,1-a]isoquinolin-7-one) which is more potent (IC₅₀ = 0.24 µM) than TIM-063 without any inhibitory activity against CaMKK isoforms and a relative AAK1-selectivity among the Numb-associated kinases family. TIM-098a could inhibit AAK1 activity in transfected cultured cells (IC₅₀ = 0.87 µM), indicating cell-membrane permeability of the compound. Overexpression of AAK1 in HeLa cells significantly reduced the number of early endosomes, which was blocked by treatment with 10 µM TIM-098a. These results indicate TIM-063-Kinobeads-based chemical proteomics is efficient for identifying off-target kinases and re-evaluating the kinase inhibitor (TIM-063), leading to the successful development of a novel inhibitory compound (TIM-098a) for AAK1, which could be a molecular probe for AAK1. TIM-098a may be a promising lead compound for a more potent, selective and therapeutically useful AAK1 inhibitor.

DOI： 10.1038/s41598-024-57051-9

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Other Link： https://www.nature.com/articles/s41598-024-57051-9

The effect of solvent molecules on crystallisation of heterotrinuclear M^II–Tb^III–M^II complexes with tripodal nonadentate ligands

Kazuma Takahara, Yuki Horino, Koki Wada, Hiromu Sakata, Daichi Tomita, Yukinari Sunatsuki, Hiroshi Isobe, Masaaki Kojima, Takayoshi Suzuki

CrystEngComm 26 ( 7 ) 1004 - 1014 2024

Crystallization Behavior of Heterotrinuclear Zn^II–Ln^III–Zn^II Complexes Bearing Two Tripodal Nonadentate Ligands: Possibility for Absolute Spontaneous Resolution

Kazuma Takahara, Yuki Horino, Koki Wada, Hiromu Sakata, Yukinari Sunatsuki, Masaaki Kojima, Takayoshi Suzuki

Crystal Growth & Design 23 ( 7 ) 5244 - 5256 2023.6

Characterization and interconversion of two crystal forms of NEt-3IB, a retinoid X receptor agonist Reviewed

Takamura, Yuta, Kikuzawa, Shota, Fujihara, Michiko, Sunatsuki, Yukinari, Higaki, Kazutaka, Kakuta, Hiroki

Chemical & Pharmaceutical Bulletin 71 ( 4 ) 282 - 288 2023.4

Structural comparison of geometrical isomers of N'-(1H-imidazol-4-ylmethylene)picolinohydrazide and their mononuclear and dinuclear cobalt(III) complexes Reviewed

Daniel K.B. Acheampong, Yukinari Sunatsuki, Takayoshi Suzuki

Results in Chemistry 5 100798 - 100798 2023.1

Selective Formation of Unsymmetric Multidentate Azine-Based Ligands in Nickel(II) Complexes Reviewed

Kennedy Mawunya Hayibor, Yukinari Sunatsuki, Takayoshi Suzuki

MOLECULES 27 ( 20 ) 6788 - 6788 2022.10

Language：English Publishing type：Research paper (scientific journal) Publisher：MDPI

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.

DOI： 10.3390/molecules27206788

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Crystal Structure of a 1,3-Diyne Iron Complex, [(eta(5)-Cp)(2)Fe-2(mu-CO) (CO) {mu, eta(1): eta(1): eta(2)-(C=O) C (C6H5)=C-C CC6H5)}]center dot 0.5 (C2H4Cl2), Formed by C-C Bond Coupling with Carbon Monoxide Reviewed

Shinsaku Yamazaki, Yukinari Sunatsuki, Tsutomu Mizuta, Toshiaki Yonemura

X-RAY STRUCTURE ANALYSIS ONLINE 38 27 - 28 2022.2

Language：English Publishing type：Research paper (scientific journal) Publisher：JAPAN SOC ANALYTICAL CHEMISTRY

The compound crystallized in a monoclinic system, and was characterized thus: space group P2(1)ln, a = 7.887(41)angstrom, b = 21.853(11)angstrom, c = 14.355(7)angstrom, beta = 100.567(4)degrees, Z = 4, V = 2432.27(28)angstrom(3). The crystal structure was solved by direct methods and refined by full-matrix least squares on F-2 to final values of R-1 = 0.0539 and wR(2) = 0.1568. 1,3-Diyne of the title compound, undergoing C-C bond coupling with carbon monoxide, cross-links to {(eta(5)-Cp)(2)Fe-2(mu-CO) (CO)(2)}-group to form a 1,2-dimetalla-3-cyclopentene-5-one by a {mu, eta(1): eta(1): eta(2))-bond fashion with atomic distances of Fe1-Fe2 2.553(1)angstrom, Fe1-C1 2.058(3)angstrom, Fe2-C2 1.945(3)angstrom, C1-C2 1.423(4)angstrom, and C1-C3 1.499(4)angstrom, respectively.

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Field-induced single-ion magnet behaviors in 1-dimensionally assembled tetrahedral cobalt(II) complexes with halide donors Reviewed

Ryoji Mitsuhashi, Satoshi Hosoya, Yukinari Sunatsuki, Takayoshi Suzuki, Masahiro Mikuriya

INORGANICA CHIMICA ACTA 529 120667 - 120667 2022.1

Language：English Publishing type：Research paper (scientific journal) Publisher：ELSEVIER SCIENCE SA

Three tetrahedral cobalt(II) complexes [CoX2(H2thp)2] were prepared and characterized (H(2)thp = 2-(1,4,5,6tetrahydropyrimidin-2-yl)phenol, X = Cl, Br, and I). X-ray crystallographic analysis indicates that the H2thp ligand coordinates to a Co ion in monodentate fashion in zwitterionic form. In the crystal, all the complexes formed characteristic one-dimensional chain structures via N-H center dot center dot center dot X hydrogen-bonding interactions. The static magnetic measurements showed that the g-factors and axial zero-field splitting parameters for Br- and I- derivatives are quite similar despite the deference in the halide ligand. A significant frequency dependence was observed for all the complexes in dynamic magnetic measurements in the presence of an external field. The relaxation dynamics below 3 K for the Br- and I- derivatives were found to be dominated by Raman relaxation process, while that of the Cl- derivative was dominated by Orbach process. The relatively long intermolecular Co center dot center dot center dot Co distances > 8 angstrom resulted in no influence in the static magnetic properties and the QTM phenomena.

DOI： 10.1016/j.ica.2021.120667

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Synthesis of Nilotinin M3: An Ellagitannin Containing an Isodehydrodigalloyl Group Reviewed

Haruka Imai, Yuta Kanzaka, Yukinari Sunatsuki, Hitoshi Abe

SYNTHESIS-STUTTGART 53 ( 19 ) 3630 - 3638 2021.10

Language：English Publishing type：Research paper (scientific journal) Publisher：GEORG THIEME VERLAG KG

Total synthesis of nilotinin M3, which is a member of the ellagitannin family of natural products containing an isodehydrodigalloyl (isoDHDG) group, was achieved using the Ullmann reaction to construct a highly functionalized diaryl ether.

DOI： 10.1055/a-1508-9541

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Versatility of coordination modes of N'-(pyridin-2-ylmethylene) picolinoylhydrazidate in the mononuclear cobalt(III) and polynuclear cobalt(II) complexes Reviewed

Daniel K. B. Acheampong, Kei Kirihara, Rina Ogawa, Yukinari Sunatsuki, Takayoshi Suzuki

INORGANICA CHIMICA ACTA 525 120464 - 120464 2021.9

Language：English Publishing type：Research paper (scientific journal) Publisher：ELSEVIER SCIENCE SA

Molecular and crystal structures of the mononuclear cobalt(III) complexes bearing N'-(pyridin-2-ylmethylene) picolinoylhydrazidate (Lpy-), [Co(Lpy)3] (1) and [Co(Lpy)2]BF4 (2a and 2b), as well as those of the Lpy-bridged CoIII2CoII trinuclear and CoII4 tetranuclear complexes, [Co3(Lpy)4(H2O)2](BF4)4 (3) and [Co4(Lpy)4Cl2(CH3CN)2] (BF4)2 (4), were determined by the single-crystal X-ray diffraction method, which revealed a variety of coordination and bridging modes of the multidentate Lpy- ligand. The protonated free hydrazone, HLpy, exists as an E-form (in regard to the imine configuration) in the solid state and in solution. In the mononuclear CoIII complexes, the hydrazonate anion (Lpy-) coordinates to a CoIII center in three different coordination modes: a bidentate kappa 2N1,N2 mode with the E-form (in 1) and two kinds of tridentate modes with the respective configuration, Z-kappa 3N1,N2,N4 and E-kappa 3O,N3,N4, in 2a and 2b. The former tridentate mode was sterically favored in the CoIII complexes, resulting in the five- and six-membered chelate rings, with a conversion of the imine configuration during the complexation. Complex 2a could also serve as a complex ligand toward a CoII ion with the kappa 2O, N3 mode, forming the CoIII-CoII-CoIII trinuclear complex (3). In the novel tetranuclear CoII complex (4), the ELpy- hydrazonates bridged two CoII ions in two different modes: mu-kappa 2O,N1:kappa 3O,N3,N4 and mu-kappa 2N1,N2:kappa 3O,N3,N4, where all chelate coordinations formed a five-membered ring with the CoII ion.

DOI： 10.1016/j.ica.2021.120464

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Zero-field slow relaxation of magnetization in cobalt(ii) single-ion magnets: suppression of quantum tunneling of magnetization by tailoring the intermolecular magnetic coupling Reviewed

Ryoji Mitsuhashi, Satoshi Hosoya, Takayoshi Suzuki, Yukinari Sunatsuki, Hiroshi Sakiyama, Masahiro Mikuriya

RSC ADVANCES 10 ( 71 ) 43472 - 43479 2020.12

Language：English Publishing type：Research paper (scientific journal) Publisher：ROYAL SOC CHEMISTRY

The correlation between magnetic relaxation dynamics and the alignment of single-ion magnets (SIMs) in a crystal was investigated using four analogous cobalt(ii) complexes with unique hydrogen-bond networks. The hydrogen-bonding interactions in the crystals resulted in a relatively short intermolecular CoMIDLINE HORIZONTAL ELLIPSISCo distance, which led to non-zero intermolecular magnetic coupling. All the complexes with a CoMIDLINE HORIZONTAL ELLIPSISCo distance shorter than 6.5 angstrom exhibited zero-field slow magnetic relaxation as weak magnetic interactions split the ground +/- M-s levels and suppressed quantum tunneling of magnetization (QTM). In particular, antiferromagnetically coupled one-dimensional chain SIM networks effectively suppressed QTM when the two intrachain CoMIDLINE HORIZONTAL ELLIPSISCo distances were non-equivalent. However, when the two distances in a chain were equivalent and each molecular symmetry axis aligned parallell within the chain, QTM suppression was insufficient because magnetic coupling from the adjacent molecules was virtually cancelled. Partial substitution of the Co-II ion with the diamagnetic Zn-II ion up to 33% for this complex resulted in complete QTM suppression in the absence of an external field. These results show that the manipulation of intermolecular distances and alignments is effective for suppressing undesired QTM events in SIMs.

DOI： 10.1039/d0ra08286d

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Sterically Demanding 8-(Diphenylphosphino)quinoline Complexes of Group 10 Metal(II): Synthesis, Crystal Structures, and Properties in Solution Reviewed

Masatoshi Mori, Yukinari Sunatsuki, Takayoshi Suzuki

INORGANIC CHEMISTRY 59 ( 24 ) 18225 - 18240 2020.12

Language：English Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

Several series of platinum(II), palladium(II), and nickel(II) complexes bearing 8-(diphenylphosphino)quinoline (PQ(H)) or its 2-methyl or 2-phenyl derivatives (PQ(Me) or PQ(Ph)) were synthesized, and their crystal structures and behaviors in solution were investigated. Most of the complexes [M(PQ(R))(2)]X-2 (M-II = P-II, Pd-II, or Ni-II; R = H, Me or Ph; X = monoanionic ions) characterized in this study have an approximately square-planar coordination geometry with two bidentate P,N-chelating or monodentate P-donating quinolylphosphine ligands in the cis(P,P) configuration. A large steric requirement from the Me or Ph substituent introduced at the 2-position of the quinoline ring gives the resulting complexes severe distortion. The Pt-II and Pd-II complex cations maintained the square-planar coordination geometry, but the M(II )center was displaced from the chelating ligand plane. This bending of the chelate coordination makes the M-N(quinoline) bond weaker, as demonstrated by the longer M-N bonds. In accord with the bond weakening, the partial dissociation of the PQ(H) or PQ(Me) chelates by substitution with halide anions were observed using UV-vis spectroscopy and X-ray crystallography. In contrast, the PQ(Ph) complexes were stable in solution toward the addition of halide anions; the intramolecular pi-pi stacking interaction between the coordinating quinolyl and the 2-substituted phenyl rings protects the M-II center from nucleophilic attack. In the corresponding Ni-II complexes, the steric congestion arising from the mutually cispositioned PQ(R) ligands resulted in a larre tetrahedral distortion around the Ni-II center. However, the intramolecular pi-pi stacking interaction was still effective in the PQ(Ph) complex, and this interaction can explain some unusual robustness and electrochemical properties of the Ni-II-PQ(Ph) complex.

DOI： 10.1021/acs.inorgchem.0c02706

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Iron(II) Complexes Having Dinuclear Mesocate or Octanuclear Bicapped Trigonal Prism Structures Dependent on the Rigidity of Bis(bidentate) Schiff Base Ligands Containing Imidazole Groups Reviewed

Tsubasa Tanaka, Yukinari Sunatsuki, Takayoshi Suzuki

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 93 ( 3 ) 427 - 437 2020.3

Language：English Publishing type：Research paper (scientific journal) Publisher：CHEMICAL SOC JAPAN

Dinuclear complex, [Fe-2(H2L1'(Me))(3)](ClO4)(4) (1Me, H(2)L1,(Me) = N,N'-(1,3 -phenylene)bis (1 -(5 -methyl-1H-imidazol-4-yl)methanimine)), and octanuclear complexes, [Fe-8(H2L2,H)(12)](ClO4)(16 )(2HClO: H2L2,H = N,N'-(1,3-phenylenebis(methylene))bis-(1-(1H-imidazol-4-yl)methanimine) and [Fe-2(H2L2'(Me))(12)](X)(16) (2MeX: H2L2,Me = N.N'-(1,3 -phenylene))bis-(methylene))bis- (1-(5-methyl-1H-imidazol-4-yl)methanimine), X = ClO4, BF4), were synthesized. It was revealed by X-ray analysis that 1Me has a dinuclear mesocate structure. On the other hand, 2HClO4 and 2MeX have novel octanuclear bicapped trigonal prism structures with six iron(II) sites having the meridional configuration on vertexes and two iron(II) sites having the facial one on the centers of each triangular base. Magnetic susceptibility studies indicated that these dinuclear and octanuclear complexes show gradual spin-crossover (SCO) behavior.

DOI： 10.1246/bcsj.20190360

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Synthesis and magnetic properties of tetrahedral tetranuclear iron(II) complexes with bis(bidentate)-type Schiff bases containing imidazole groups Reviewed

Tsubasa Tanaka, Yukinari Sunatsuki, Takayoshi Suzuki

INORGANICA CHIMICA ACTA 502 119373 - 119373 2020.3

Language：English Publishing type：Research paper (scientific journal) Publisher：ELSEVIER SCIENCE SA

Two new tetranuclear iron(II) complexes, [Fe-4(H2LH)(6)](ClO4)(8) (1ClO(4): H2LH = N,N'-bis(imidazole-4-ylmethylidene)-1.4-diaminobenzene) and [Fe-4(H2LMe)(6)](BF4)(8) (2BF(4): H2LMe = N,N'-bis(5-methylimidazole-4-ylmethylidene)-1.4-diaminobenzene), were synthesized from Fe(ClO4 or BF4)(2)center dot 6H(2)O, 1.4-diaminobenzene and 4-formylimidazole or 5-methyl-4-formylimidazole. X-ray analysis revealed that these complexes have a tetrahedral structure with four iron(II) ions at the apexes and the bridging bis(bidentate) ligands on the edges. The internal space of the tetrahedron was filled with the phenylene segments of the bridging ligands. Magnetic susceptibility studies indicated that both 1ClO(4) and 2BF(4) showed gradual but incomplete spin-crossover (SCO) behavior, because the densely packed tetrahedral structure could prevent the contraction of the Fe-N bonds on the highspin to low-spin transition.

DOI： 10.1016/j.ica.2019.119373

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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 Reviewed

Misaki Matsushima, Koki Wada, Yuki Horino, Kazuma Takahara, Yukinari Sunatsuki, Takayoshi Suzuki

CRYSTENGCOMM 22 ( 3 ) 458 - 466 2020.1

Language：English Publishing type：Research paper (scientific journal) Publisher：ROYAL SOC CHEMISTRY

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), [M-II(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 P2(1)2(1)2(1), 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 Lambda-form vs. right-handed Delta-form complex cations) in all cases. Moreover, in the cases of Ni-II and Zn-II 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.

DOI： 10.1039/c9ce01864f

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Tetra- and dinuclear manganese complexes of xanthene-bridged O,N,O-Schiff bases with 3-hydroxypropyl or 2-hydroxybenzyl groups: ligand substitution at a triply bridging site Reviewed

Ogawa Rina, Suzuki Takayoshi, Hirotsu Masakazu, Nishi Noriyuki, Shimizu Yuu, Sunatsuki Yukinari, Teki Yoshio, Kinoshita Isamu

DALTON TRANSACTIONS 48 ( 36 ) 13622 - 13629 2019.9

Hydrogen-bonding interactions and magnetic relaxation dynamics in tetracoordinated cobalt(ii) single-ion magnets Reviewed

Mitsuhashi Ryoji, Hosoya Satoshi, Suzuki Takayoshi, Sunatsuki Yukinari, Sakiyama Hiroshi, Mikuriya Masahiro

DALTON TRANSACTIONS 48 ( 2 ) 395 - 399 2019.1

trans-Dichloridotetrakis(pyridine-κN)rhodium(III) chloride methanol tetrasolvate Reviewed

Takayoshi Suzuki, Misaki Tsujino, Yukinari Sunatsuki

IUCrData 3 ( 10 ) x181482 2018.10

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