Photoluminescent cuprous iodide polymorphs generated via in situ organic reactions

Low-Dimensional Hybrid Cuprous Halides Directed by Transition Metal Complex: Syntheses, Crystal Structures, and Photocatalytic Properties

“…It is worth noting that the tetrahedral [CuI 4 ] unit often undergoes a variety of self-condensation to form polyanions of cluser or oligomer as SBUs. However, most of the SBUs are self-condensed to form 1D anionic chains, such as [Cu 2 X 3 ] − , [Cu 2 X 4 ] 2– , [Cu 3 X 4 ] − , [Cu 3 X 6 ] 3– , [Cu 4 X 6 ] 2– , [Cu 5 X 7 ] 2– , and [Cu 6 X 7 ] − , etc. − Occasionally, these SBUs can also be interlinked to form 2D microporous layers; for example, two isomeric 2D [Cu 11 I 17 ] 6– layers are composed of [Cu 3 I 7 ], [Cu 4 I 8 ], [Cu 6 I 12 ], and [Cu 12 I 22 ] units in [De-DABCO] 2 [Me-DABCO]­Cu 11 I 17 . Undoubtedly, the 2D [Cu 6 I 11 ] 5– layer reported here based on trimeric [Cu 3 I 7 ] building blocks represents a new microporous layer in hybrid iodocuprate chemistry.…”

“…Generally speaking, the Cu­(I) ion is able to adopt myriad coordination geometries including linear CuX 2 , CuX 3 triangle, and CuX 4 tetrahedron (X = Br, I). More interestingly, the tetrahedral CuX 4 unit features high self-assembly characterization and diversiform condensation modes including corner- and edge-sharing as well as short Cu···Cu interactions. , To date, numerous [Cu x X y ] (y–x)– anionic clusters or secondary building units (SBUs) have been characterized including binuclear [Cu 2 X 3 ] − , [Cu 2 X 4 ] 2– , and [Cu 2 X 6 ] 4– ; trinuclear [Cu 3 X 7 ] 4– and [Cu 3 X 8 ] 5– ; tetranuclear [Cu 4 X 6 ] 2– , [Cu 4 I 8 ] 4– , [Cu 4 X 9 ] 5– , and [Cu 4 X 11 ] 7– ; pentanuclear [Cu 5 X 7 ] 2– ; hexanuclear [Cu 6 I 10 ] 4– and [Cu 6 I 11 ] 5– , and even larger [Cu 8 I 13 ] 5– and [Cu 36 I 56 ] 20‑ units, etc. − Using these clusters or SBUs as building blocks, a large amount of 1D chains including [Cu 2 X 3 ] − , [Cu 2 X 4 ] 2– , [Cu 3 X 4 ] − , [Cu 3 X 6 ] 3– , [Cu 4 X 6 ] 2– , [Cu 5 X 7 ] 2– , and [Cu 6 X 7 ] − , etc., and 2D layers of [Cu 3 I 4 ] − , [Cu 4 I 5 ] − , and [Cu 11 I 17 ] 6– , etc., have also been reported and characterized. − Relatively, three-dimensional (3D) frameworks are rarely documented with limited topological networks.…”

Ultrasensitive Photochromic Iodocuprate(I) Hybrid

“…Single crystal X-ray analysis reveals that 1 crystallizes in the orthorhombic space group Pbca and its asymmetric unit has four copper­(I) atoms, six iodine atoms, and one MNH 2+ dication (Figure S1). The structure of 1 contains two similar [Cu 2 I 3 ] n n – chains composed of edge- and face-shared CuI 4 tetrahedra (chains A and B as shown in Figure b), analogous to the chains observed in [N­(CH 3 ) 4 ]­[Cu 2 I 3 ] . Two chains present slightly different conformations with different Cu–I bond lengths, I–Cu–I bond angles, and Cu···Cu separations due to the distinct environments provided by MNH 2+ counterions (Figure c).…”

“…The single crystal XRD and PXRD data for 1 and 1P (Tables S1 and S2 and Figure S2) have ruled out the possible structural change after light irradiation. The solid UV–vis diffuse reflectance spectrum of 1 at 298 K shows broad absorption in the range of 420–600 nm, which corresponds to the brown-yellow color of 1 (Figure b) and implies an intense intermolecular charge transfer (CT) between MNH 2+ cations and [Cu 2 I 3 ] n n – anions with respect to that of colorless [N­(CH 3 ) 4 ]­[Cu 2 I 3 ]. , Comparatively, 1P as an irradiated product displays a new broader absorption band in the range of 500–780 nm in the UV–vis spectrum. Meanwhile, the EPR spectra of 1 and the decolored sample display small signals (Figure c), which should be caused by indoor light during sample handling due to the high photosensitivity of 1 as supported by its responses to further light irradiation and heating in vacuo (see photochromic part and Supporting Information).…”