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These ligands play a key role in the formation of various copper(I) cyanide systems, including one-dimensional (1D) chains, two-dimensional (2D) layers and three-dimensional (3D) frameworks. According to the literature, numerous coordination polymers based on terminal, \u03bc<jats:sub>2<\/jats:sub>-<jats:italic>C<\/jats:italic>:<jats:italic>N<\/jats:italic> and \u03bc<jats:sub>3<\/jats:sub>-<jats:italic>C<\/jats:italic>,<jats:italic>C<\/jats:italic>,<jats:italic>N<\/jats:italic> bridging modes have been documented so far. However, systems based on the \u03bc<jats:sub>4<\/jats:sub>-<jats:italic>C<\/jats:italic>:<jats:italic>C<\/jats:italic>:<jats:italic>N<\/jats:italic>:<jats:italic>N<\/jats:italic> bridging mode are relatively rare. In this work, a novel cyanide-bridged 3D Cu<jats:sup>I<\/jats:sup> coordination framework, namely poly[(\u03bc<jats:sub>2<\/jats:sub>-2,2\u2032-biimidazole-\u03ba<jats:sup>2<\/jats:sup>\n                  <jats:italic>N<\/jats:italic>\n                  <jats:sup>3<\/jats:sup>:<jats:italic>N<\/jats:italic>\n                  <jats:sup>3\u2032<\/jats:sup>)(\u03bc<jats:sub>4<\/jats:sub>-cyanido-\u03ba<jats:sup>4<\/jats:sup>\n                  <jats:italic>C<\/jats:italic>:<jats:italic>C<\/jats:italic>:<jats:italic>N<\/jats:italic>:<jats:italic>N<\/jats:italic>)(\u03bc<jats:sub>2<\/jats:sub>-cyanido-\u03ba<jats:sup>2<\/jats:sup>\n                  <jats:italic>C<\/jats:italic>:<jats:italic>N<\/jats:italic>)dicopper(I)], [Cu<jats:sub>2<\/jats:sub>(CN)<jats:sub>2<\/jats:sub>(C<jats:sub>6<\/jats:sub>H<jats:sub>6<\/jats:sub>N<jats:sub>4<\/jats:sub>)]<jats:sub>\n                     <jats:italic>n<\/jats:italic>\n                  <\/jats:sub>, (I), was synthesized hydrothermally by reaction of environmentally friendly K<jats:sub>3<\/jats:sub>[Fe(CN)<jats:sub>6<\/jats:sub>], CuCl<jats:sub>2<\/jats:sub>\u00b72H<jats:sub>2<\/jats:sub>O and 2,2\u2032-biimidazole (H<jats:sub>2<\/jats:sub>biim). It should be noted that cyanide ligands may act as reducing agents to reduce Cu<jats:sup>II<\/jats:sup> to Cu<jats:sup>I<\/jats:sup> under hydrothermal conditions. Compound (I) contains diverse types of bridging ligands, such as \u03bc<jats:sub>4<\/jats:sub>-<jats:italic>C<\/jats:italic>:<jats:italic>C<\/jats:italic>:<jats:italic>N<\/jats:italic>:<jats:italic>N<\/jats:italic>-cyanide, \u03bc<jats:sub>2<\/jats:sub>-<jats:italic>C<\/jats:italic>:<jats:italic>N<\/jats:italic>-cyanide and \u03bc<jats:sub>2<\/jats:sub>-biimidazole. Interestingly, the [Cu<jats:sub>2<\/jats:sub>] dimers are bridged by rare \u03bc<jats:sub>4<\/jats:sub>-<jats:italic>C<\/jats:italic>:<jats:italic>C<\/jats:italic>:<jats:italic>N<\/jats:italic>:<jats:italic>N<\/jats:italic>-mode cyanide ligands giving rise to the first example of a 1D dimeric {[Cu<jats:sub>2<\/jats:sub>(\u03bc<jats:sub>4<\/jats:sub>-<jats:italic>C<\/jats:italic>:<jats:italic>C<\/jats:italic>:<jats:italic>N<\/jats:italic>:<jats:italic>N<\/jats:italic>)]<jats:sup>\n                     <jats:italic>n<\/jats:italic>+<\/jats:sup>}<jats:sub>\n                     <jats:italic>n<\/jats:italic>\n                  <\/jats:sub> infinite chain. Furthermore, adjacent dimer-based chains are linked by \u03bc<jats:sub>2<\/jats:sub>-<jats:italic>C<\/jats:italic>:<jats:italic>N<\/jats:italic> bridging cyanide ligands, generating a neutral 2D wave-like (4,4) layer structure. Finally, the 2D layers are joined together <jats:italic>via<\/jats:italic> bidentate bridging H<jats:sub>2<\/jats:sub>biim to create a 3D cuprous cyanide network. This arrangement leads to a systematic variation in dimensionality from 1D chain\u21922D sheet\u21923D framework by different types of bridging ligands. Compound (I) was further characterized by thermal analysis, solid-state UV\u2013Vis diffuse-reflectance and photoluminescence studies. The solid-state UV\u2013Vis diffuse-reflectance spectra show that compound (I) is a wide-gap semiconductor with band gaps of 3.18\u2005eV. The photoluminescence study shows a strong blue\u2013green photoluminescence at room temperature, which may be associated with metal-to-ligand charge transfer.<\/jats:p>","DOI":"10.1107\/s2053229619014025","type":"journal-article","created":{"date-parts":[[2019,10,24]],"date-time":"2019-10-24T12:28:42Z","timestamp":1571920122000},"page":"1517-1523","update-policy":"https:\/\/doi.org\/10.1107\/cm_01","source":"Crossref","is-referenced-by-count":5,"title":["A novel three-dimensional copper(I) cyanide coordination polymer constructed from various bridging ligands: synthesis, crystal structure and characterization"],"prefix":"10.1107","volume":"75","author":[{"given":"Ying-Lian","family":"Qin","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Hong","family":"Sun","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yan","family":"Jing","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Xiu-Ping","family":"Jiang","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Gao-Feng","family":"Wang","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jian-Fang","family":"Qin","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"329","published-online":{"date-parts":[[2019,10,23]]},"reference":[{"key":"yo3064_bb1","doi-asserted-by":"crossref","first-page":"174","DOI":"10.1021\/ic801509t","volume":"48","author":"Bayse","year":"2009","journal-title":"Inorg. 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