Semiconducting Coordination Polymers Based on the Predesigned Ternary Te-Fe-Cu Carbonyl Cluster and Conjugation-Interrupted Dipyridyl Linkers.

A series of semiconducting cluster-incorporated Cu-based coordination polymers, namely, 1D zigzag polymers [{TeFe3 (CO)9 Cu2 }(L)]n (L=1,2-bis(4-pyridyl)ethane (bpea), 1; L=1,2-bis(4-pyridyl)ethylene (bpee), 5), 2D honeycomb-like polymers [{TeFe3 (CO)9 Cu}Cu(L)2.5 ]n (L=bpea, 2; L=bpee, 6), and 2D wave-like cation-anion polymer [{Cu2 (L)4 }({TeFe3 (CO)9 Cu}2 (L))]n (L=1,3-bis(4-pyridyl)propane (bpp), 4), as well as the macrocycle [{TeFe3 (CO)9 Cu2 }2 (bpp)2 ] (3) have been quantitatively synthesized via the liquid-assisted grinding from the pre-designed cluster [TeFe3 (CO)9 Cu2 (MeCN)2 ] with conjugated or conjugation-interrupted dipyridyl linkers. Notably, the most conjugation-interrupted bpp-bridged polymer 4 exhibited extraordinary semiconducting characteristics with an ultra-narrow bandgap of 1.43 eV and a DC conductivity of 1.5×10-2 Ω-1  cm-1 , which violates our knowledge, mainly attributed to the through-space electron transport via non-classical C-H⋅⋅⋅O(carbonyl) hydrogen bonds and aromatic C-H⋅⋅⋅π interactions. The incorporated Te-Fe-CO anions can not only provide numerous possibilities for secondary interactions within these Cu-based polymers but also serve as a redox-active coordination ligand to promote their conductivities. The intriguing structure-property relationships were studied by X-ray and DFT analyses and further demonstrated by significant change in the oxidation state of Cu atoms by XPS and Cu K-edge XANES.

Copper-incorporated mono- and di-TeRu5 metal carbonyl complexes: syntheses, structures, and an unusual skeletal arrangement.

Two sandwich-type Cu3Cl- or Cu2{Te2Ru4(CO)10}-bridging di-TeRu5 clusters, [{TeRu5(CO)14}2Cu3Cl](2-) () and [{TeRu5(CO)14}2Cu2{Te2Ru4(CO)10}](4-) (), were obtained from the reaction of [TeRu5(CO)14](2-) with 1 equiv. of [Cu(MeCN)4][BF4] in CH2Cl2 or THF at 0 °C, respectively, depending on the solvents. The chloride-abstracted was structurally characterized to have two TeRu5 cores that were linked by a Cu3Cl moiety with two Cu-Cu bonds. If the reaction was carried out in a molar ratio of 1 : 2 at 0 or 30 °C in CH2Cl2, the structural isomers [TeRu5(µ-CO)2(CO)12(CuMeCN)2] () and [TeRu5(µ-CO)3(CO)11Cu2(MeCN)2] () were produced, respectively, as the major product. Cluster displayed a TeRu5 core with two adjacent Ru3 triangles each capped by a µ3-Cu(MeCN) fragment, while contained a TeRu5 core with one triangle Ru3 plane capped by a Cu2(MeCN)2 fragment with two Cu atoms covalently bonded. Upon heating, the isomerization of into proceeded to undergo an unusual skeletal arrangement of Cu(MeCN) and migration of CO, with the TeRu5 core remaining intact. An electrochemical study revealed that and each exhibited only one oxidation while cluster had two consecutive oxidations, suggesting significant electronic communication between the two TeRu5 metal cores in via the Cu3 moiety. This work describes the facile synthesis of a series of semiconducting Cux-bridging Te-Ru carbonyl clusters, in which the incorporation of the Cux fragments has significantly influenced their resulting structures, rearrangements, and electronic properties, which was further elucidated by DFT calculations.

Stepwise construction of manganese-chromium carbonyl chalcogenide complexes: synthesis, electrochemical properties, and computational studies.

When trigonal-bipyramidal clusters, [PPN][E(2)Mn(3)(CO)(9)] (E = S, Se), were treated with Cr(CO)(6) and PPNCl in a molar ratio of 1:1:2 or 1:2:2 in 4 M KOH/MeCN/MeOH solutions, mono-Cr(CO)(5)-incorporated HE(2)Mn(3)-complexes [PPN](2)[HE(2)Mn(3)Cr(CO)(14)] (E = S, [PPN](2)[1a]; Se, [PPN](2)[1b]), respectively, were formed. X-ray crystallographic analysis showed that 1a and 1b were isostructural and each displayed an E(2)Mn(3) square-pyramidal core with one of the two basal E atoms externally coordinated with one Cr(CO)(5) group and one Mn-Mn bond bridged by one hydrogen atom. However, when the TMBA(+) salts for [E(2)Mn(3)(CO)(9)](-) were mixed with Cr(CO)(6) in a molar ratio of 1:1 in 4 M KOH/MeOH solutions and refluxed at 60 °C, mono-Cr(CO)(3)-incorporated E(2)Mn(3)Cr octahedral clusters [TMBA](3)[E(2)Mn(3)Cr(CO)(12)] (E = S, [TMBA](3)[2a]; Se, [TMBA](3)[2b]), respectively, were obtained. Clusters 2a and 2b were isostructural, and each consisted of an octahedral E(2)Mn(3)Cr core, in which each Mn-Mn or Mn-Cr bond of the Mn(3)Cr plane was semibridged by one carbonyl ligand. Clusters 1a and 1b (with [TMBA] salts) underwent metal core closure to form octahedral clusters 2a and 2b upon treatment with KOH/MeOH at 60 °C. In addition, 1a and 1b were found to undergo cluster expansion to form di-Cr(CO)(5)-incorporated HE(2)Mn(3)-clusters [HE(2)Mn(3)Cr(2)(CO)(19)](2-) (E = S, 3a; Se, 3b), respectively, upon the addition of 1 or 2 equiv of Cr(CO)(6) heated in refluxing CH(2)Cl(2). Clusters 3a and 3b were structurally related to clusters 1a and 1b, but with the other bare E atom (E = S, 3a; Se, 3b) further externally coordinated with one Cr(CO)(5) group. The nature, cluster transformation, and electrochemical properties of the mixed manganese-chromium carbonyl sulfides and selenides were systematically discussed in terms of the chalcogen elements, the introduced chromium carbonyl group, and the metal skeleton with the aid of molecular calculations at the BP86 level of the density functional theory.

Chromium-manganese selenide carbonyl complexes: paramagnetic clusters and relevance to C=O activation of acetone.

The paramagnetic even-electron cluster, [Et(4)N](2)[Se(2)Cr(3)(CO)(10)], was found to react readily with Mn(CO)(5)Br in acetone to produce two unprecedented mixed chromium-manganese selenide carbonyl complexes, [Et(4)N][Me(2)CSe(2){Mn(CO)(4)}{Cr(CO)(5)}(2)] ([Et(4)N][1]) and [Et(4)N](2)[Se(2)Mn(3)(CO)(10){Cr(CO)(5)}(2)] ([Et(4)N](2)[2]). X-ray crystallographic analysis showed that anion 1 consisted of two Se-Cr(CO)(5) moieties, which were further bridged by one isopropylene group and one Mn(CO)(4) moiety. The dianionic cluster 2 was shown to display a Se(2)Mn(3) square-pyramidal core with each Se atom externally coordinated by one Cr(CO)(5) group. The formation of complex 1, presumably via C=O activation of acetone, was further facilitated by acidification of the reaction of [Et(4)N](2)[Se(2)Cr(3)(CO)(10)] with Mn(CO)(5)Br in acetone. Complex 1 readily transformed into 2 upon treatment with Mn(2)(CO)(10) in a KOH/MeOH/MeCN solution. Cluster 2 was a 51-electron species, which readily converted to the known 49-electron cluster [Se(2)Mn(3)(CO)(9)](2-) upon heating and bubbling with CO. Magnetic studies of the even-electron cluster, [Et(4)N](2)[Se(2)Cr(3)(CO)(10)], and the odd-electron species, [Et(4)N](2)[2] and [PPN](2)[Se(2)Mn(3)(CO)(9)], were determined by the SQUID measurement to have 2, 3, and 1 unpaired electrons, respectively. In addition, the nature and formation of complexes 1 and 2 are discussed, and the magnetic properties and electrochemistry of [Se(2)Cr(3)(CO)(10)](2-), 2, and [Se(2)Mn(3)(CO)(9)](2-) were further studied and elucidated by molecular orbital calculations at the PW91 level of density functional theory.

Bimetallic Ru-Cu tellurido complexes: controlled synthesis and electrochemical studies of copper halide-TeRu(5) and Te(2)Ru(4) clusters.

When [TeRu(5)(CO)(14)](2-) () was treated with 1 equiv. of CuX (X = Cl, Br, I) in THF, mono-CuX-TeRu(5) clusters [TeRu(5)(CO)(14)CuX](2-) (X = Cl, ; Br, ; I, ) were obtained. Clusters consist of an octahedral TeRu(5) core, in which one triangular Ru(3) plane is capped by a mu(3)-CuX fragment. For CuX (X = Cl, Br), the reaction of complex with 2 equiv. of CuX in THF at room temperature formed Cu(4)X(2)-linked di-TeRu(5) clusters [{TeRu(5)(CO)(14)}(2)Cu(4)X(2)](2-) (X = Cl, ; Br, ), while the same reaction in MeCN at -35 degrees C produced bis-CuX-TeRu(5) complexes [TeRu(5)(CO)(14)(CuX)(2)](2-) (X = Cl, ; Br, ). X-Ray analysis showed that displays a TeRu(5) core with two adjacent Ru(3) triangles each capped by a mu(3)-CuBr ligand while has two TeRu(5) cores that are linked by a mu(6)-Cu(4)Br(2) moiety. Clusters and underwent coupling reactions in THF to yield clusters and , and easily transformed to bis-CuX-Te(2)Ru(4) clusters [Te(2)Ru(4)(CO)(10)(CuX)(2)](2-) (X = Cl, ; X = Br, ) in MeCN. On the other hand, the reaction of with 2 equiv. of CuI in THF directly produced the bis-CuI-Te(2)Ru(4) cluster [Te(2)Ru(4)(CO)(10)(CuI)(2)](2-) (). The nature, stability, stepwise cluster transformation, and electrochemistry of these CuX-incorporated TeRu(5)- and Te(2)Ru(4)-based complexes are discussed systematically. In particular, the effects of CuX and the metal cores (TeRu(5)vs. Te(2)Ru(4)) on the resultant Te-Ru-Cu clusters are further elucidated by molecular orbital calculations at the B3LYP level of the density functional theory.

Semiconducting tellurium-iron-copper carbonyl polymers.

The unprecedented ternary Te-Fe-Cu chain polymers [{Et4N}{TeFe3(CO)9Cu}]infinity and [{TeFe3(CO)9Cu2}(mu-4,4'-dipyridyl)1.5]infinity were prepared from the self-assembly of [Et4N]2[TeFe3(CO)9] with [Cu(MeCN)4][BF4] in THF or in the presence of 4,4'-dipyridyl in THF. These two chain polymers, which can also be constructed from the precursor complex TeFe3(CO)9Cu2(MeCN)2, show semiconducting behaviors with low band gaps of 0.59 and 0.41 eV, respectively. In addition, their conductivity and the effect of the bridging ligand are further elucidated by theoretical calculations.

Construction of copper halide-triiron selenide carbonyl complexes: synthetic, electrochemical, and theoretical studies.

A new family of CuX-, Cu(2)X(2)-, and Cu(4)X(2)-incorporated mono- or di-SeFe(3)-based carbonyl clusters were constructed and structurally characterized. When the selenium-capped triiron carbonyl cluster [Et(4)N](2)[SeFe(3)(CO)(9)] was treated with 1-3 equiv of CuX in tetrahydrofuran (THF) at low or room temperatures, CuX-incorporated SeFe(3) complexes [Et(4)N](2)[SeFe(3)(CO)(9)CuX] (X = Cl, [Et(4)N](2)[1a]; Br, [Et(4)N](2)[1b]; I, [Et(4)N](2)[1c]), Cu(2)X(2)-incorporated SeFe(3) clusters [Et(4)N](2)[SeFe(3)(CO)(9)Cu(2)X(2)] (X = Cl, [Et(4)N](2)[2a]; Br, [Et(4)N](2)[2b]), and Cu(4)X(2)-linked di-SeFe(3) clusters [Et(4)N](2)[{SeFe(3)(CO)(9)}(2)Cu(4)X(2)] (X = Cl, [Et(4)N](2)[3a]; Br, [PPh(4)](2)[3b]) were obtained, respectively, in good yields. SeFe(3)CuX complexes 1a and 1b were found to undergo cluster expansion to form SeFe(3)Cu(2)X(2) complexes 2a and 2b, respectively, upon the addition of 1 equiv of CuX (X = Cl, Br). Furthermore, complexes 2a and 2b can expand further to form Cu(4)X(2)-linked di-SeFe(3) clusters 3a and 3b, upon treatment with 1 equiv of CuX (X = Cl, Br). [Et(4)N](4)[{SeFe(3)(CO)(9)(CuCl)(2)}(2)] ([Et(4)N](4)[4a]) was produced when the reaction of [Et(4)N](2)[SeFe(3)(CO)(9)] with 2 equiv of CuCl was conducted in THF at 40 degrees C. The Cu(2)Cl(2)-linked di-SeFe(3)CuCl cluster 4a is a dimerization product derived from complex 2a. Further, it is found that complex 4a can convert to the Cu(4)Cl(2)-linked di-SeFe(3) cluster 3a upon treatment with CuCl. The nature, formation, stepwise cluster expansion, and electrochemical properties of these CuX-, Cu(2)X(2)-, and Cu(4)X(2)-incorporated mono- or di-SeFe(3)-based clusters are elucidated in detail by molecular calculations at the B3LYP level of the density functional theory in terms of the effects of selenium, iron, copper halides, and the size of the metal skeleton.

Copper halide-bridged ruthenium telluride carbonyl complexes: discovery of the semiconducting cluster chain polymer {[PPh4]2[Te2Ru4(CO)10Cu4Br2Cl2].THF}infinity.

A new series of Te-Ru-Cu carbonyl complexes was prepared by the reaction of K(2)TeO(3) with [Ru(3)(CO)(12)] in MeOH followed by treatment with PPh(4)X (X=Br, Cl) and [Cu(MeCN)(4)]BF(4) or CuX (X=Br, Cl) in MeCN. When the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was first treated with PPh(4)X followed by the addition of [Cu(MeCN)(4)]BF(4), doubly CuX-bridged Te(2)Ru(4)-based octahedral clusters [PPh(4)](2)[Te(2)Ru(4)(CO)(10)Cu(2)X(2)] (X=Br, [PPh(4)](2)[1]; X=Cl, [PPh(4)](2)[2]) were obtained. When the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was treated with PPh(4)X (X=Br, Cl) followed by the addition of CuX (X=Br, Cl), three different types of CuX-bridged Te-Ru carbonyl clusters were obtained. While the addition of PPh(4)Br or PPh(4)Cl followed by CuBr produced the doubly CuBr-bridged cluster 1, the addition of PPh(4)Cl followed by CuCl led to the formation of the Cu(4)Cl(2)-bridged bis-TeRu(5)-based octahedral cluster compound [PPh(4)](2)[{TeRu(5)(CO)(14)}(2)Cu(4)Cl(2)] ([PPh(4)](2)[3]). On the other hand, when the reaction mixture of K(2)TeO(3) and [Ru(3)(CO)(12)] was treated with PPh(4)Br followed by the addition of CuCl, the Cu(Br)CuCl-bridged Te(2)Ru(4)-based octahedral cluster chain polymer {[PPh(4)](2)(Te(2)Ru(4)(CO)(10)Cu(4)Br(2)Cl(2)).THF}(infinity) ({[PPh(4)](2)[4].THF}(infinity)) was produced. The chain polymer {[PPh(4)](2)[4].THF}(infinity) is the first ternary Te-Ru-Cu cluster and shows semiconducting behavior with a small energy gap of about 0.37 eV. It can be rationalized as resulting from aggregation of doubly CuX-bridged clusters 1 and 2 with two equivalents of CuCl or CuBr, respectively. The nature of clusters 1-4 and the formation and semiconducting properties of the polymer of 4 were further examined by molecular orbital calculations at the B3LYP level of density functional theory.