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Simple room-temperature self-assemblies between Cd2+ salts, SCN− and bisimidazole molecules at pH = 2 created three new organically templated thiocyanatocadmates [H2(L1)][Cd(SCN)4]·H2O (L1 = 1,4-bis(1H-imidazol-1-yl)benzene) 1, [H2(L2)][Cd(SCN)4] (L2 = 1,3-bis(2-methylimidazol-1-yl)propane) 2, and [H2(L3)][Cd2(SCN)6] (L3 = 1,4-bis(2-methyl-1H-imidazol-1-yl)butane) 3. X-ray single-crystal diffraction analysis reveals that (i) in 1–3, the SCN− groups doubly bridge the Cd2+ centers to form different thiocyanatocadmates: a linear chain in 1; a zigzag chain in 2; and a 2-D layer network (63 net) in 3; and (ii) in 1, via Nbase–H…NSCN interactions, the L1 molecules extend the thiocyanatocadmate chains into a 2-D supramolecular layer, whereas in 2, the zigzag thiocyanatocadmate chains self-assemble into a 3-D supramolecular network via weak S…S interactions. Photoluminescence analysis indicates that the three title compounds all emit light: blue light for 1 and 2 and green light for 3. At low temperatures, the emission positions of the three compounds hardly change, but the emission intensities are largely enhanced. Interestingly, after turning off the UV lamp, 1 and 2 still briefly emit light (ca. 2 s), which means that 1 and 2 possess phosphorescence properties. Phosphorescence lifetimes at 77 K are 1619 ms for 1 and 247 ms for 2. [ABSTRACT FROM AUTHOR]

Based on an aim of introducing the SCN − or SO 4 2 − group into the organically templated chlorocadmates, a series of room-temperature reactions at pH 2 were performed, creating four new Cd(II) hybrids as [L1] 4 [Cd 4 Cl 6 (SCN) 10 (H 2 O) 2 ] (L1 = 1,1′-dibenzyl-4,4′-bipyridium) 1 , [H 4 L2][CdCl 4 (SCN) 2 ] (L2 = 1,4-bis(4-pyridylmethyl)piperazine) 2 , [HL3] 3 [CdCl 3 ]SO 4 (L3 = 2-amino-6-chloropyridine) 3 , and [HL4] 3 [CdCl 3 ]SO 4 (L4 = 2-amino-6-bromopyridine) 4 . X-ray single-crystal diffraction analysis reveals that (i) templated by L1 2+ , 1 shows a 1-D single-chain structure, which is based on the dinuclear [Cd 2 Cl 3 (SCN) 4 (H 2 O)] 3 − clusters by the μ-1,3-mode SCN − groups; (ii) templated by H 4 L2 4+ , 2 only exhibits a mononuclear structure. However, via the intermolecular weak N pyridine H⋯Cl, N piperazine H⋯Cl and S SCN ⋯S SCN interactions, 2 self-assembles into a 3-D supramolecular network with a (4,6)-connected topology; (iii) 3 and 4 possess the similar structures. Via the N pyridine/amino H⋯O and π⋯π interactions, the introduced SO 4 2 − groups and the organic base molecules aggregate together into a 3-D supramolecular network with the 1-D channels. Within the channel, the Cl − ions triplely bridge the Cd 2+ centers into a 1-D linear [CdCl 3 ] − chain. Based on the structural information and the previous related reports, the role of the introduced SCN − or SO 4 2− group in the hybrid is revealed. SCN − acts as two roles: (i) a linker; (ii) a cutter. Sometimes SO 4 2− serves as a linker, while sometimes SO 4 2− connects with organic base into a supramolecular aggregation, acting as a new templating agent. The photoluminescence analysis reveals that 2 , 3 and 4 emit light with the maxima at 535 nm for 2 ( λ ex = 465 nm), 462 nm for 3 ( λ ex = 428 nm), and 465 nm for 4 ( λ ex = 430 nm), respectively. In particular, the emissions for all are strong, and can be seen under the ultraviolet (UV) lamp. [ABSTRACT FROM AUTHOR]