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 [{TeFe (CO) Cu }(L)] (L=1,2-bis(4-pyridyl)ethane (bpea), 1; L=1,2-bis(4-pyridyl)ethylene (bpee), 5), 2D honeycomb-like polymers [{TeFe (CO) Cu}Cu(L) ] (L=bpea, 2; L=bpee, 6), and 2D wave-like cation-anion polymer [{Cu (L) }({TeFe (CO) Cu} (L))] (L=1,3-bis(4-pyridyl)propane (bpp), 4), as well as the macrocycle [{TeFe (CO) Cu } (bpp) ] (3) have been quantitatively synthesized via the liquid-assisted grinding from the pre-designed cluster [TeFe (CO) Cu (MeCN) ] 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.

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.

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.

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.

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.

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).

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.

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.