Three novel cation-templated metal thiocyanates with 1-2D polypseudorotaxane frameworks

Qiao, Yong-Zhen; Yue, Junming; Liu, Xiu-Cun; Niu, Yun‐Yin

doi:10.1039/c1ce05528c

Cited by 27 publications

(9 citation statements)

References 32 publications

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“…By isolating the Na + cation, the Na···S interaction was removed, but no extended structure was observed in 4 – 7 , suggesting that the electrostatic repulsion of linking a string of anions prevents the formation of a 1D array, not the steric hindrance of the Na cation. There are numerous examples in the literature of (SCN) as a bridging ligand between anions in which the charge-balancing cations are of the form iminium, − R 4 N + , and even [Cu(terpy) 2 ] 2+ . Thus, one needs both steric access to the Pt site as well as sufficient electrophilicity.…”

Section: Resultsmentioning

confidence: 99%

Thiocyanate-Ligated Heterobimetallic {PtM} Lantern Complexes Including a Ferromagnetically Coupled 1D Coordination Polymer

et al. 2016

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A series of heterobimetallic lantern complexes with the central unit {PtM(SAc)4(NCS)} have been prepared and thoroughly characterized. The {Na(15C5)}[PtM(SAc)4(NCS)] series, 1 (Co), 2 (Ni), 3 (Zn), are discrete compounds in the solid state, whereas the {Na(12C4)2)}[PtM(SAc)4(NCS)] series, 4 (Co), 5 (Ni), 6 (Zn), and 7 (Mn), are ion-separated species. Compound 7 is the first {PtMn} lantern of any bridging ligand (carboxylate, amide, etc.). Monomeric 1-7 have M(2+), necessitating counter cations that have been prepared as {(15C5)Na}(+) and {(12C4)2Na}(+) variants, none of which form extended structures. In contrast, neutral [PtCr(tba)4(NCS)]∞ 8 forms a coordination polymer of {PtCr}(+) units linked by (NCS)(-) in a zigzag chain. All eight compounds have been thoroughly characterized and analyzed in comparison to a previously reported family of compounds. Crystal structures are presented for compounds 1-6 and 8, and solution magnetic susceptibility measurements are presented for compounds 1, 2, 4, 5, and 7. Further structural analysis of dimerized {PtM} units reinforces the empirical observation that greater charge density along the Pt-M vector leads to more Pt···Pt interactions in the solid state. Four structural classes, one new, of {MPt}···{PtM} units are presented. Solid state magnetic characterization of 8 reveals a ferromagnetic interaction in the {PtCr(NCS)} chain between the Cr centers of J/kB = 1.7(4) K.

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Section: Resultsmentioning

confidence: 99%

Thiocyanate-Ligated Heterobimetallic {PtM} Lantern Complexes Including a Ferromagnetically Coupled 1D Coordination Polymer

et al. 2016

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“…[Cu 2 (SCN) 4 ]} n , in which DIBP was used as a template. 15 Although the formula of [Ag 2 (SCN) 4 ] n 2n− in 6 is the same with those of 2 and 4, their structures differ to some extent. As described above, in 2 and 4, terminal SCN − anions are observed in the Ag 2 SCN 6 dimer and hexagonal ring.…”

Section: The Interlayer S•••s Distance Is Long Enough To Rule Out The...mentioning

confidence: 99%

“…16,49 The organic viologen can generally emit at about 400 nm. 15,16 Therefore, only the metal-to-ligand charge transfer (MLCT) can explain these red emissions, among which electrons transfers from Ag centers to π antibonding orbitals of SCN − moieties have occurred. 53,54 Upon compression, two different trends of their emissions can be found.…”

Section: The Interlayer S•••s Distance Is Long Enough To Rule Out The...mentioning

confidence: 99%

Two-Dimensional Silver-Thiocyanate Layers Directed by Viologens: Structural Transformations upon Low Pressure Stimuli, Piezochromic Luminescence, Photocurrent Responses, and Photocatalytic Properties

Song

Zhao

Zhang

et al. 2018

Crystal Growth & Design

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The reactions of AgSCN with excess KSCN in the presence of linear viologens templates afford seven new hybrids, {(MV)[Ag4(SCN)6]} n (1), {(MV)[Ag2(SCN)4]} n (2), {(EV)[Ag4(SCN)6]} n (3), {(EV)[Ag2(SCN)4]} n (4), {(BV)[Ag4(SCN)6]} n (5), {(CMV)[Ag2(SCN)4]} n (6), and {(BMPE)[Ag2(SCN)4]} n (7) (MV2+ = methyl viologen, EV2+ = ethyl viologen, BV2+ = benzyl viologen, CMV2+ = cyanomethyl viologen, BMPE2+ = 1,2-bis(N-methylpyridiniim-4-yl)ethane). The silver-thiocyanate skeletons with the formula of [Ag4(SCN)6] n 2n– and [Ag2(SCN)4] n 2n– are the scarce representative examples of the two-dimensional (2-D) polypseudorotaxane arrays penetrated (for 1–6) or intercalated (for 7) by viologen dications. Upon an external low pressure stimulus, the 2-D silver-thiocyanate layers penetrated by cations exhibit looser packing with longer Ag–S(N) bond lengths, weaker charge transfer (CT) interactions, and larger cavities, but the contrary trend can be found on the compound with intercalated organic cations. Due to the strong CT interactions between viologens and silver-thiocyanate skeletons, the CTs can occur at room temperature. Interestingly, 7 represents typical reversible piezochromic luminescence behavior. In addition, they show excellent photocurrent responses and efficient photocatalytic degeneration performances on organic dyes. Finally, their band structures and density of states before and after compression based on density functional theory calculations were executed to correlate their properties.

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“…In our recent studies, the construction of a 1D supramolecular rotaxane polymer {(BPE) 3 [Ag 4 Br 4 (SCN) 6 ]} n induced by organic cation 1,2-bis (pyridinium ethane) dibromide (BPE) has been reported. 17 We therefore decided to modify our approach by using the different linear components with new capping groups. Accordingly, we designed BMLB as a suitable linear component for incorporation within a pseudorotaxane.…”

Section: Introductionmentioning

confidence: 99%

Role of cooperative templates in the self-assembly process of microporous structures: syntheses and characterization of 12 new silver halide/thiocyanate supramolecular polymers

Qiao

Yue

et al. 2012

CrystEngComm

Self Cite

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12 new cation-templated complexes, {(BMPB)[AgI 3 ]} (BMPB ¼ 1, 4-bis (methylpyridinium) benzene) 12), have been synthesized via the self-assembly reaction in solution. Owing to the cooperative template effects from organic cations and halide/thiocyanate anion compounds 1-11 contain a mononuclear anion structure [AgI 3 ] 2À (1), a dimeric anion [Ag 2 I 6 ] 4À (2), linear chain [Ag 2 X 4 ] 2À (3-10) and a cubanelike based one-dimensional anionic chain [Ag 4 I 6 ] 2À (11) that are enclosed into the different cationic channels formed from the pyridinium, phenanthrolinium and imidazolium. While for 12, the compound possesses an infinite 2D supramolecular polypseudorotaxane penetrated by geminal dicationic groups.

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Three novel cation-templated metal thiocyanates with 1-2D polypseudorotaxane frameworks

Cited by 27 publications

References 32 publications

Thiocyanate-Ligated Heterobimetallic {PtM} Lantern Complexes Including a Ferromagnetically Coupled 1D Coordination Polymer

Thiocyanate-Ligated Heterobimetallic {PtM} Lantern Complexes Including a Ferromagnetically Coupled 1D Coordination Polymer

Two-Dimensional Silver-Thiocyanate Layers Directed by Viologens: Structural Transformations upon Low Pressure Stimuli, Piezochromic Luminescence, Photocurrent Responses, and Photocatalytic Properties

Role of cooperative templates in the self-assembly process of microporous structures: syntheses and characterization of 12 new silver halide/thiocyanate supramolecular polymers

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