耐晒大红BBN与表面活性剂双组分光催化降解

以表面活性剂十六烷基三甲基溴化铵(CTAB)和难溶有机颜料耐晒大红BBN(简称BBN)为双组分降解底物, 以TiO2为光催化剂, 研究双组分底物的光催化降解的快慢及规律, 双组分降解的相互影响, 初步建立双组分和催化剂之间的作用模型. 结果表明, pH值及底物的浓度对双组分体系的降解都有显著影响, 碱性条件更适合体系的降解, 在中性(pH=6.8)环境中两种底物的降解效果明显高于单组分的降解. 在碱性条件下(pH=9.2), 加入BBN使CTAB的降解速率略有下降. CTAB的浓度对BBN褪色速率影响较大, 当CTAB 的浓度为1 cmc 时, BBN和CTAB的降解速率都达到最快. BBN在TiO2表面吸附性强, 且被优先降解.     

Ligand design for alkali-metal-templated self-assembly of unique high-nuclearity CuII aggregates with diverse coordination cage units: crystal structures and properties

The construction of two unique, high-nuclearity Cu(II) supramolecular aggregates with tetrahedral or octahedral cage units, [(mu(3)-Cl)[Li subset Cu(4)(mu-L(1))(3)](3)](ClO(4))(8)(H(2)O)(4.5) (1) and [[Na(2) subset Cu(12)(mu-L(2))(8)(mu-Cl)(4)](ClO(4))(8)(H(2)O)(10)(H(3)O(+))(2)](infinity) (2) by alkali-metal-templated (Li(+) or Na(+)) self-assembly, was achieved by the use of two newly designed carboxylic-functionalized diazamesocyclic ligands, N,N'-bis(3-propionyloxy)-1,4-diazacycloheptane (H(2)L(1)) or 1,5-diazacyclooctane-N,N'-diacetate acid (H(2)L(2)). Complex 1 crystallizes in the trigonal R3c space group (a = b = 20.866(3), c = 126.26(4) A and Z = 12), and 2 in the triclinic P1 space group (a = 13.632(4), b = 14.754(4), c = 19.517(6) A, alpha = 99.836(6), beta = 95.793(5), gamma = 116.124(5) degrees and Z = 1). By subtle variation of the ligand structures and the alkali-metal templates, different polymeric motifs were obtained: a dodecanuclear architecture 1 consisting of three Cu(4) tetrahedral cage units with a Li(+) template, and a supramolecular chain 2 consisting of two crystallographically nonequivalent octahedral Cu(6) polyhedra with a Na(+) template. The effects of ligand functionality and alkali metal template ions on the self-assembly processes of both coordination supramolecular aggregates, and their magnetic behaviors are discussed in detail.     

Sandwich-type transition metal complexes [(CBO)n]2M with carbon boronyl ligands (CBO)n (n=4–6)

A density functional theory investigation on a series of sandwich-type transition metal complexes [(CBO)_n]₂M (n=4–6; M=transition metals) with carbon boronyls (CBO)_n as effective aromatic ligands has been presented in this work at B3LYP level. The ground-states of these complexes possess staggered D_nd symmetries, while the corresponding eclipsed D_nh structures exist as transition states with slightly higher energies (within 5.8 kJ/mol). Carbon boronyl complexes [(CBO)_n]₂M are confirmed to be much more stable than their boron carbonyl isomers [(BCO)_n]₂M, which, on the other hand, take eclipsed ground-states with D_nh symmetries. The carbon boronyl complexes [(BCO)_n]₂M proposed in this work parallelize the well-known sandwich-type hydrocarbon complexes [C_nH_n]₂M in coordination chemistry with boronyl groups –BO isolobal to –H atoms in corresponding ligands.     

新型有序结构分子聚集体的构筑

本文概述了近年来我们在新型有序结构分子聚集体构筑方面取得的一些主要成绩，并展望了今后进一步的研究和发展方向。     

A unique cyanide-bridged three-dimensional (3-D) copper(II)-copper(I) mixed-valence polymer containing 1-D water tapes with cyclic pentamer units

A unique cyano-bridged copper(II)-copper(I) mixed-valence polymer, {[Cu(3)(CN)(4)(H(2)O)(3)](H(2)O)(2)}(n) (1), has been prepared and structurally determined by X-ray diffraction. The cyanide anions with (mu(2),eta(2)) and (mu(3),eta(2)) bridging modes connect the copper centers into a complicated zeolite-like 3-D network. Of further interest, coordinated and lattice water molecules in this structure form 1-D hydrogen-bonded water tapes consisting of linked cyclic pentamer clusters.     

Nickel-manganese sulfido carbonyl cluster complexes. synthesis, structure, and properties of the unusual paramagnetic complexes Cp2Ni2Mn(CO)3(mu 3-E)2, E = S, Se

The reaction of Mn(2)(CO)(7)(mu-S(2)) with [CpNi(CO)](2) yielded the paramagnetic new compound Cp(2)Ni(2)Mn(CO)(3)(mu(3)-S)(2) (1) and a new hexanuclear metal product Cp(2)Ni(2)Mn(4)(CO)(14)(mu(6)-S(2))(mu(3)-S)(2) (2). Structurally, compound 1 contains two triply bridging sulfido ligands on opposite sides of an open Ni(2)Mn triangular cluster. EPR and temperature-dependent magnetic susceptibility measurements of 1 show that it contains one unpaired electron. The electronic structure of 1 was determined by Fenske-Hall molecular orbital calculations which show that the unpaired electron occupies a low lying antibonding orbital delocalized unequally across the three metal atoms. The selenium homologue Cp(2)Ni(2)Mn(CO)(3)(mu(3)-Se)(2) (3) was obtained from the reaction of a mixture of Mn(2)(CO)(10) and [CpNi(CO)](2) with elemental selenium and Me(3)NO.2H(2)O. It also has one unpaired electron. Compound 1 reacted with elemental sulfur to yield the dinickeldimanganese compound, Cp(2)Ni(2)Mn(2)(CO)(6)(mu(4)-S(2))(mu(4)-S(5)), 4, which can also be made from the reaction of Mn(2)(CO)(7)(mu-S(2)) with [CpNi(CO)](2) and sulfur. Compound 4 was converted back to 1 by sulfur abstraction using PPh(3). The reaction of Mn(2)(CO)(10) with [CpNi(CO)](2) in the presence of thiirane yielded the ethanedithiolato compound CpNiMn(CO)(3)(mu-SCH(2)CH(2)S) (5), which was also obtained from the reaction of Mn(4)(CO)(15)(mu(3)-S(2))(mu(4)-S(2)) with [CpNi(CO)](2) in the presence of thiirane. Compound 5 reacted with additional quantities of thiirane to yield the new compound CpNiMn(CO)(3)[mu-S(CH(2)CH(2)S)(2)], 6, which contains a 3-thiapentanedithiolato ligand that bridges the two metal atoms. Compound 6 was also obtained from the reaction of Mn(2)(CO)(10) with [CpNi(CO)](2) and thiirane. The molecular structures of the new compounds 1-6 were established by single-crystal X-ray diffraction analyses.     

New Ni(II)Cu(II)Ni(II) trinuclear complexes with an 5=3/2 high-spin ground

Four new heterotrinuclear complexes have been synthesized and characterized, namely {[Ni(L)₂]₂[Cu(opba)]}(ClO₄)₂, where opba denotes o-phenylenebis(oxamato) and L stands for 1,10-phenanthroline(phen) (1), 5-nitro-l,10-phenanthroline(NO₂-phen) (2), 2,2′-bipyridyl(bpy) (S) and 4,4′-dimethyl-2,2′-bipyridyl(Me₂bpy) (4). The temperature dependence of the magnetic susceptibility of {[Ni(phen)₂]₂[Cu(opba)]}(ClO₄)₂3H₂O has been studied in the 4–300 K range, giving the exchange integral J—109 cm^?1. The HMT vs. T plot exhibits a minimum at about 100 K, characteristic of this kind of coupled polymetallic complex with an irregular spin-state structure.     

Z‐bpy,a New C2‐Symmetric Bipyridine Ligand and Its Application in Enantioselective Copper(I)‐Catalyzed Cyclopropanation of Olefins

A rigid C₂‐symmetric chiral bipyridine ligand Z‐bpy with a triptycene‐like backbone was designed and synthesized from simple chemicals in a scalable route. Using this new ligand, copper(I) catalyzed cyclopropanation of styrenes with commercial ethyl diazoacetate produced various corresponding cyclopropanes in high yields, diastereoselectivity and enantioselectivity up to 97% ee.