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 1.5×10 Ω cm , 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.

Mixed bismuth–chalcogen–iron clusters [{EFe3(CO)9}­Bi]− [E = Te (1a) or Se (1b)] were produced via the reduction of BiCl3 with [EFe3(CO)9]2– under mild conditions. X-ray analysis showed that both clusters 1a and 1b had a square-pyramidal geometry, where the naked Bi and chalcogen both adopted a distorted trigonal-pyramidal configuration with a stereoactive lone pair. Complexes 1a and 1b can be further functionalized by methylation and metalation, which permits the nucleophilicity of the 6s/5s and 6s/4s lone pairs to be compared. In the metalation, the 6s pair of the Bi atom in 1a and 1b had an extraordinary nucleophilicity toward the unsaturated Cr­(CO)5 fragment, even in the presence of the more chemically active 5s or 4s pair, whereas in the case of methylation, only the 4s pair of Se could be selectively alkylated. Upon oxidation of 1a and 1b with suitable oxidizing agents, NaBiO3 or K2SeO3, Bi–E bonded tetrahedral complexes [{EFe2(CO)6}­Bi]− [E = Te (4a) or Se (4b)] were formed by the elimination of one Fe­(CO)3 vertex. X-ray photoelectron spectroscopy, X-ray absorption near-edge structure, and density functional theory (DFT) calculations showed that all of the Bi atoms in these complexes had oxidation states close to +1. Due to the electropositive character of the Bi atom, pronounced induced Bi···E inter- and intramolecular interactions were evident in 1a (1b), 4a (4b), and the metalated 3a (3b), where their linear-like ···Bi···E··· or zigzag-like ···Bi–E··· (E = Te or Se) chain or the Bi···E···E···Bi (E = Te or Se) dimeric chain can further expand into the two-dimensional network via nonclassical C–H···O­(carbonyl) interactions, supported by noncovalent interaction index and DFT calculations. These positively charged Bi-induced Bi···E (E = Te or Se) and carbonyl-aided weak interactions can facilitate efficient electron transport within these ternary Bi–E–Fe or quaternary Bi–E–Fe–Cr cluster-based frameworks, resulting in semiconducting behavior with surprising ultranarrow energy gaps of 1.01–1.21 eV.

The reactions of E powder (E=S, Se) with a mixture of Cr(CO)6 and Mn2(CO)10 in concentrated solutions of KOH/MeOH produced two new mixed Cr-Mn-carbonyl clusters, [E2CrMn2(CO)9](2-) (E=S, 1; Se, 2). Clusters 1 and 2 were isostructural with one another and each displayed a trigonal-bipyramidal structure, with the CrMn2 triangle axially capped by two μ3-E atoms. The analogous telluride cluster, [Te2CrMn2(CO)9](2-) (3), was obtained from the ring-closure of Te2Mn2 ring complex [Te2Mn2Cr2(CO)18](2-) (4). Upon bubbling with CO, clusters 2 and 3 were readily converted into square-pyramidal clusters, [E2CrMn2(CO)10](2-) (E=Se, 5; Te, 6), accompanied with the cleavage of one Cr-Mn bond. According to SQUID analysis, cluster 6 was paramagnetic, with S=1 at room temperature; however, the Se analogue (5) was spectroscopically proposed to be diamagnetic, as verified by TD-DFT calculations. Cluster 6 could be further carbonylated, with cleavage of the Mn-Mn bond to produce a new arachno-cluster, [Te2CrMn2(CO)11](2-) (7). The formation and structural isomers, as well as electrochemistry and UV/Vis absorption, of these clusters were also elucidated by DFT calculations.

A new type of TeFe3(CO)9-incorporated dicopper NHC complex was obtained directly from one-pot reactions. By the introduction of the cluster anion [TeFe3(CO)9](2-) and NHCs as the ligands, these di-Cu(i)-based complexes exhibited pronounced catalytic activities toward the homocoupling of arylboronic acids with low Cu loadings and high yields (up to 98%).