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Abstract: A multifunctional ligand of 4,8-disulfonyl-2,6-naphthalenedicarboxylic acid (H4-DSNDA) and its Eu(III) coordination polymer {(H-dpp)[Eu(DSNDA)(H2O)4](H2O)4}n (dpp=1,3-di(4-pyridyl)propane) (1) have been synthesized. Compound 1 is a 2D anionic network based on the paddle-wheel Eu2(CO2)4 building blocks charge-balanced by the monoprotonated H-dpp molecules. Compound 1 shows intense red characteristic europium(III)-centered emission. The Eu(III) emissive state exhibits a single-exponential decay with a lifetime of 0.212ms as measured at 613nm after excitation at 346nm. No observable emission peak arising from the DSNDA4− ligand (λem =408nm) is observed in the emission spectrum of compound 1, indicating an efficient energy transfer occurs from DSNDA4− organic ligand to Eu(III) ions. The results reveal the large π-rich aromatic organic ligand is a suitable chromophoric moiety for sensitization of Eu(III) luminescence. [Copyright &y& Elsevier]

Abstract: Compound {(EMIM)2[Zn7(μ4-O)2(1,4-ndc)6]}n (1) (EMIM=1-ethyl-3-methylimidazolium and 1,4-ndc=1,4-naphthalenedicarboxylate) has been synthesized by using the mixed ionic liquids of 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium l-lactate as solvent. Compound 1 has a 3D anionic framework with bcu-(424·64) topology based on a unique heptanuclear [Zn7(μ4-O)(μ2-COO)10] cluster as secondary building unit. The imidazolium cation [EMIM]+ of the ionic liquid acting as extra framework charge-balancing species occupies the channels of the 3D anionic framework. The roles of the ionic liquid in ionothermal synthesis and crystallization of compound 1 are briefly discussed. The thermal and photoluminescent properties of compound 1 have also been investigated. [Copyright &y& Elsevier]

Abstract: Two coordination polymers, namely, [Co(IM)6][Co2(SIP)3] (1) (IM=imidazole, H3SIP=5-sulfoisophthalic acid) and [BMIM]2[Cd2(SIP)3] (2) (BMIM=1-n-butyl-3-methylimidazolium) were synthesized in ionothermal reactions by using ionic liquid 1-n-butyl-3-methylimidazolium tetrafluoroborate as solvent. Single-crystal X-ray analyses revealed that 1 has an anionic 1D polymeric chain charge balanced by an uncommon [Co(IM)6]2+ cation. Complex 2 features an anionic 2D layer containing unique tetranuclear [Cd4(CO2)6(SO3)2] cluster wherein the four Cd atoms are co-planar. The imidazolium cation [BMIM]+ of the ionic liquid acting as charge compensating agent intercalated into the [Cd2(SIP)2]2n− interlayers in structure 2. The rich ionic environments of the ionic liquid may be particularly helpful in the formation of the anionic frameworks of 1 and 2. [Copyright &y& Elsevier]

A 3D coordination polymer [CdK 6 (μ 2 -H 2 O) 2 (BODSDC) 2 (H 2 O)] n ( 1 ) based on the novel benzophenone-3,3′-disulfonyl-4,4′-dicarboxylate (BODSDC 4− ) ligand was synthesized and structurally characterized. The carboxylate and sulfonate groups of the organic ligands as well as the bridging water molecules connect the Cd 2+ and K + ions to produce a 2D layer, which is linked by the benzophenone moieties to give a 3D pillared framework. Compound 1 crystallizes in an acentric space group of Cc and has a large second-harmonic-generation (SHG) response of 1.3 times that of potassium dihydrogen phosphate (KDP) in the particle size of 25–210 μm. Further SHG measurements revealed that the material is type-I phase-matchable. The observed SHG efficiency is associated with the unsymmetrical geometry of the organic ligand and the distorted coordination polyhedrons of metal centers. [ABSTRACT FROM AUTHOR]

Two isomorphous compounds [Eu(2,2′-bpdc)(NO3)(e-urea)3]n (1) and [Tb(2,2′-bpdc)(NO3)(e-urea)3]n (2) (2,2′-bpdc2−=2,2′-biphenyldicarboxylate and e-urea=ethyleneurea) have been synthesized using a deep-eutectic solvent of choline chloride/e-urea. The lanthanide ions are linked by the 2,2′-bpdc2− ligands to form one-dimensional helical chains in these compounds. Of special interest is the presence of parallel left- and right-handed single helices with the ratio of 1:1 in both compounds. Detailed photoluminescence studies show that both compounds exhibit typical lanthanide luminescent emissions and the excitation energy has been efficiently transferred to the lanthanide ions from the organic ligands. [ABSTRACT FROM AUTHOR]

A three-dimensional structure [Zn(H-ntb)] n (1) constructed from the tetrahedrally coordinated Zn(II) atoms and 4,4′,4′'-nitrilotribenzoate ligands was presented. Compound 1 exhibits a phase-matchable second-harmonic-generation response of 1.2 times that of KDP. • A noncentrosymmetric coordination network. • A compound constructed from the 4,4′,4′'-nitrilotribenzoate. • Helical chains based on the 4,4′,4′'-nitrilotribenzoate and [ZnO 4 ] tetrahedrons. • A 3D zinc compound exhibits a large SHG response. A coordination polymer [Zn(H-ntb)] n (1) based on the tritopic carboxylate linker of 4,4′,4′'-nitrilotribenzoate (H 3 -ntb) was reported here. Compound 1 crystallizes in a polar space group of Pca 2 1 and contains two-dimensional layers formed from the left- and right-handed helical chains pillared by the benzoate moieties to give a three-dimensional structure. The present compound 1 features a noncentrosymmetric structure and displays a strong phase-matchable second-harmonic-generation (SHG) response of 1.2 times that of potassium dihydrogen phosphate (KDP). The inherent polarity of the 4,4′,4′'-nitrilotribenzoate and distortive [ZnO 4 ] tetrahedrons as well as the asymmetric arrangement of the building blocks are responsible for the SHG activity for 1. [ABSTRACT FROM AUTHOR]