An efficient route to construct three-dimensional (3-D) M/S/Cu nest-cluster-based coordination polymers has been developed. By this method, cyanide bridges have been successfully introduced to build three new non-interpenetrating 3-D nest-shaped-cluster [MoOS3Cu3]-based coordination polymers, 3 ∞{[(NO3)⊂(Me4N)3]⊂[MoOS3Cu3(CN)3]} (1) and 3 ∞{[(NH4)·2DMF]⊂[Mo2O2S6Cu6(CN)3(L)4]} (L1 = bipy = 4,4′-bipyridine, 2; L2 = bpee = 1,2-bis(4-pyridyl)ethene, 3). The structures of 1−3 have been established by elemental analysis, IR, UV−vis, and single-crystal X-ray crystallographic studies. 1 is the first non-interpenetrating 3-D 6-connected M/S/Cu coordination polymer and possesses an unprecedented dual-inclusive structure, rare “ACS” topology and huge free volume. 2 and 3 possess unusual non-interpenetrating 3-D pillar-layer-alternating honeycomb-like frameworks with diamondoid topologies. Nonlinear optical (NLO) properties of these clusters were investigated by Z-scan employing 5 ns pulses at 532 nm, with 1−3 showing strong third-order NLO properties. Time-dependent density functional theory (TD-DFT) studies have afforded insight into the electronic transitions and spectral characterization of these functionalized NLO molecular materials.

A not‐so‐innocent counterion: A facile synthetic method has been successfully developed to construct two unusual discrete, octanuclear planar “open” distorted‐square M/S/Ag clusters {[Sr(DMAC)6]2[M4S16Ag4]} (M=Mo, W; DMAC=N,N'‐dimethylacetylamide) and a unique 1D double‐chain W/S/Ag cluster {[Sr(DMAC)6][W2S8Ag4I2]}n (see figure). Z‐scan experiments show that {[Sr(DMAC)6]2[Mo4S16Ag4]} exhibits strong third‐order non‐linear optical properties and a large optical limiting capability.

The synthesis of fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-C≡C-1-C6H2-3,5-Et2-4-C≡CC6H4-4-C≡CH)}3] (10), which bears pendant ethynyl groups, and its reaction with [RuCl(dppe)2]PF6 to afford the heterobimetallic complex fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-C≡C-1-C6H2-3,5-Et2-4-C≡CC6H4-4-C≡C-trans-[RuCl(dppe)2])}3] (11) is described. Complex 10 is available from the two-step formation of iodo-functionalized fac-tris[2-(4-iodophenyl)pyridine]iridium(III) (6), followed by ligand-centered palladium-catalyzed coupling and desilylation reactions. Structural studies of tetrakis[2-(4-iodophenyl)pyridine-N,C1′](μ-dichloro)diiridium 5, 6, fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-C≡C-1-C6H2-3,5-Et2-4-C≡CH)}3] (8), and 10 confirm ligand-centered derivatization of the tris(2-phenylpyridine)iridium unit. Electrochemical studies reveal two (5) or one (6–10) Ir-centered oxidations for which the potential is sensitive to functionalization at the phenylpyridine groups but relatively insensitive to more remote derivatization. Compound 11 undergoes sequential Ru-centered and Ir-centered oxidation, with the potential of the latter significantly more positive than that of Ir(N,C′-NC5H4-2-C6H4-2)3. Ligand-centered π–π* transitions characteristic of the Ir(N,C′-NC5H4-2-C6H4-2)3 unit red-shift and gain in intensity following the iodo and alkynyl incorporation. Spectroelectrochemical studies of 6, 7, 9, and 11 reveal the appearance in each case of new low-energy LMCT bands following formal IrIII/IV oxidation preceded, in the case of 11, by the appearance of a low-energy LMCT band associated with the formal RuII/III oxidation process. Emission maxima of 6–10 reveal a red-shift upon alkynyl group introduction and arylalkynyl π-system lengthening; this process is quenched upon incorporation of the ligated ruthenium moiety on proceeding to 11. Third-order nonlinear optical studies of 11 were undertaken at the benchmark wavelengths of 800 nm (fs pulses) and 532 nm (ns pulses), the results from the former suggesting a dominant contribution from two-photon absorption, and results from the latter being consistent with primarily excited-state absorption.

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The present study describes the designed synthesis, X-ray structures, and magnetic properties of two 3D cyanobridged heterobimetallic tungsten/molybdenum(IV)-copper(II) MOFs, {[μ 4 -M(CN) 8 ]Cu 2 (DPP) 4 } n (M=W 1, Mo 2; DPP = 1,3-Di(4-pyridyl)propane). Both MOFs 1 and 2 were constructed by interdiffusion approach in two steps: the first reaction of CuSCN and NH 4 SCN with the flexible bridging ligand DPP in polar solvent for building a 2D homometallic Cu polymer, and the thereafter conformation of 3D heterobimetallic MOF architectures with [M(CN) 8 ] 3and 2D coordination networks. MOFs 1 and 2 are isomorphous and both crystallize in the tetragonal system and have space group I4 1 /a, with unit cell constants a=19.734(3) A ˚, b= 19.734(3) A ˚, c = 13.989(2) A ˚for 1, and a=19.7429(19) A ˚, b = 19.7429(19) A ˚, c = 13.9883(15) A ˚for 2. Our study demonstrates that such heterobimetallic MOFs possess a unique 2D f 3D architecture and exhibit a new 2-nodal topological structure. The magnetic measurement of MOFs shows typical paramagnetic properties and weak ferromagnetic interactions.

Treatment of molecular building block [W(CN) 8 ] 3À with Co(NO 3 ) 2 $6H 2 O or Cu(ClO 4 ) 2 $6H 2 O in different reaction conditions affords two 3D (three-dimensional) metalloligand-bridged coordination polymers {[W V (CN) 8 Co 2 (DMF) 8 ][NO 3 ]} n 1 and {W IV (CN) 8 Cu 2 (py) 8 } n 2, respectively. The singlecrystal X-ray structural analysis shows that both polymers 1 and 2 crystallize in the tetragonal crystal system with space group of I4 1 /a and possess the similar 3D framework in a diamondoid topology geometry, although [W(CN) 8 ] 3À ion was reduced into [W(CN) 8 ] 4À in polymer 2 during the reaction process. The magnetic studies on coordination polymers 1 and 2 indicate that polymer 1 shows the typical ferromagnetic property with an ordering temperature of about 5 K but polymer 2 exhibits paramagnetic behavior due to the diamagnetic octacyanometalate bridge -NC-W IV (S ¼ 0)-CN-.

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