Introducing Benzene-1,3,5-tri(dithiocarboxylate) as a Multidentate Linker in Coordination Chemistry.

Benzene-1,3,5-tri(dithiocarboxylate) (BTDTC3-), the sulfur-donor analogue of trimesate (BTC3-, benzene-1,3,5-tricarboxylate), is introduced, and its potential as a multidentate, electronically bridging ligand in coordination chemistry is evaluated. For this, the sodium salt Na3BTDTC has been synthesized, characterized, and compared with the sodium salt of the related ditopic benzene-1,4-di(dithiocarboxylate) (Na2BDDTC). Single-crystal X-ray diffraction of the respective tetrahydrofuran (THF) solvates reveals that such multitopic aromatic dithiocarboxylate linkers can form both discrete metal complexes (Na3BTDTC·9THF) and (two-dimensional) coordination polymers (Na2BDDTC·4THF). Additionally, the versatile coordination behavior of the novel BTDTC3- ligand is demonstrated by successful synthesis and characterization of trinuclear Cu(I) and hexanuclear Mo(II)2 paddlewheel complexes. The electronic structure and molecular orbitals of both dithiocarboxylate ligands as well as their carboxylate counterparts are investigated by density functional theory computational methods. Electrochemical investigations suggest that BTDTC3- enables electronic communication between the coordinated metal ions, rendering it a promising tritopic linker for functional coordination polymers.

[1]  Ju Li,et al.  Two-Dimensional Silver(I)-Dithiocarboxylate Coordination Polymer Exhibiting Strong Near-Infrared Photothermal Effect. , 2019, Inorganic chemistry.

[2]  Fu-Rong Chen,et al.  Integration of a (–Cu–S–)n plane in a metal–organic framework affords high electrical conductivity , 2019, Nature Communications.

[3]  Miao Meng,et al.  Electronic Coupling and Electron Transfer between Two Mo2 Units through meta- and para-Phenylene Bridges. , 2019, Chemistry.

[4]  Krishnendu Maity,et al.  Electrically Conductive Metal-Organic Frameworks , 2018 .

[5]  N. Mitzel,et al.  Dithiocarboxylic Acids: An Old Theme Revisited and Augmented by New Preparative, Spectroscopic and Structural Facts. , 2018, Chemistry.

[6]  Travis A. White,et al.  Visible-Light-Driven Photosystems Using Heteroleptic Cu(I) Photosensitizers and Rh(III) Catalysts To Produce H2. , 2018, Inorganic chemistry.

[7]  Gang He,et al.  Organic Thiocarboxylate Electrodes for a Room-Temperature Sodium-Ion Battery Delivering an Ultrahigh Capacity. , 2017, Angewandte Chemie.

[8]  A. Walsh,et al.  Metallic Conductivity in a Two-Dimensional Cobalt Dithiolene Metal-Organic Framework. , 2017, Journal of the American Chemical Society.

[9]  Mircea Dincă,et al.  Electrically Conductive Porous Metal-Organic Frameworks. , 2016, Angewandte Chemie.

[10]  Miao Meng,et al.  Tuning the Electronic Coupling and Electron Transfer in Mo2 Donor-Acceptor Systems by Variation of the Bridge Conformation. , 2016, Chemistry.

[11]  V. Chandrasekhar,et al.  Molecular metal phosphonates. , 2015, Chemical reviews.

[12]  Wei‐Xiong Zhang,et al.  Metal Cluster-Based Functional Porous Coordination Polymers , 2015 .

[13]  Daoben Zhu,et al.  A two-dimensional π–d conjugated coordination polymer with extremely high electrical conductivity and ambipolar transport behaviour , 2015, Nature Communications.

[14]  I. Smolyaninov,et al.  Compactly Fused o‐Quinone‐Extended Tetrathiafulvalene‐o‐Quinone Triad – a Redox‐Amphoteric Ligand , 2014 .

[15]  A. R. Paital,et al.  Synthesis and structures of perthio- and polymeric metal complexes with the tetrathio- and dithioterephthalate ligands , 2013 .

[16]  X. Xiao,et al.  Control of the charge distribution and modulation of the class II-III transition in weakly coupled Mo2-Mo2 systems. , 2013, Inorganic chemistry.

[17]  C. Bielawski,et al.  Assessing the proton affinities of N,N'-diamidocarbenes. , 2013, The Journal of organic chemistry.

[18]  S. Batten,et al.  Coordination polymers of sulphur-donor ligands , 2013 .

[19]  Shu Seki,et al.  Mn2(2,5-disulfhydrylbenzene-1,4-dicarboxylate): a microporous metal-organic framework with infinite (-Mn-S-)∞ chains and high intrinsic charge mobility. , 2013, Journal of the American Chemical Society.

[20]  Y. Miura,et al.  Syntheses of Sulfo-Glycodendrimers Using Click Chemistry and Their Biological Evaluation , 2012, Molecules.

[21]  M. Cokoja,et al.  Dicarboxylate-bridged (Mo2)n (n = 2, 3, 4) paddle-wheel complexes: potential intermediate building blocks for metal-organic frameworks. , 2011, Dalton transactions.

[22]  M. Yamashita,et al.  Electroconductive porous coordination polymer Cu[Cu(pdt)2] composed of donor and acceptor building units. , 2009, Inorganic chemistry.

[23]  P. Tian,et al.  Enhanced electronic coupling in a molecular pair of dimolybdenum units bridged by a tetrathioterephthalate dianion. , 2009, Inorganic chemistry.

[24]  C. Malliakas,et al.  Novel coordination polymers based on the tetrathioterephthalate dianion as the bridging ligand. , 2007, Inorganic chemistry.

[25]  M. Chisholm,et al.  Electronic coupling in 1,4-(COS)2C6H4 linked MM quadruple bonds (M = Mo, W): the influence of S for O substitution. , 2006, Dalton transactions.

[26]  J. Tomasi,et al.  Quantum mechanical continuum solvation models. , 2005, Chemical reviews.

[27]  F. Cotton,et al.  Modifying electronic communication in dimolybdenum units by linkage isomers of bridged oxamidate dianions. , 2003, Journal of the American Chemical Society.

[28]  F. Cotton,et al.  Polyunsaturated dicarboxylate tethers connecting dimolybdenum redox and chromophoric centers: syntheses, structures, and electrochemistry. , 2003, Journal of the American Chemical Society.

[29]  N. Handy,et al.  Dynamic correlation , 2001 .

[30]  G. Scuseria,et al.  An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules , 1998 .

[31]  T. Dunning,et al.  Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions , 1992 .

[32]  T. H. Dunning.  Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen , 1989 .

[33]  Mark S. Gordon,et al.  Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements , 1982 .

[34]  J. Pople,et al.  Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules , 1972 .

[35]  J. Pople,et al.  Self‐Consistent Molecular‐Orbital Methods. IX. An Extended Gaussian‐Type Basis for Molecular‐Orbital Studies of Organic Molecules , 1971 .

[36]  David,et al.  Gaussian basis sets for use in correlated molecular calculations . Ill . The atoms aluminum through argon , 1999 .