Theoretical research on the spin-Hamiltonian parameters of the square-planar CuS46− clusters in Cu(II)–dithiophosphonate complexes

The spin-Hamiltonian parameters (g-factors g_//, g_⊥ and hyperfine structure constants A_//, A_⊥) of the square-planar CuS^{6 ?}₄ clusters in Cu(II)–bis [4-ethoxphenyl-O-alkyl]-dithiophosphonate complexes are computed with the high-order perturbation formulas based on the two-mechanism model. The model includes the contributions to spin-Hamiltonian parameters from the vastly-utilised crystal-field (CF) mechanism concerning the CF excited states and the generally-omitted charge-transfer (CT) mechanism due to CT excited states. The energy levels of CF and CT excited states needed in the calculation are obtained from the observed optical spectra. The calculated results are in rational accordance with the experimental values. The signs of constants A_// and A_⊥ are suggested and the reasons of the very small g-shifts |?g_i| (= | g_i ? g_e |, where g_e ≈ 2.0023 and i = // or ⊥) are discussed.     

吡嗪基联吡啶锌配位聚合物的结构及发光性质

以2,6-双(2-吡嗪基)-4,4'-联吡啶为配体,对苯二甲酸为辅助配体,水热条件下合成了锌配位聚合物[Zn(dpb)(p-bdc)]n·0.5n(dpb),并用元素分析、红外光谱、X射线单晶衍射对此配位聚合物进行了测试分析.单晶结构解析表明,它是通过对苯二甲酸桥连锌离子形成一维链结构的配位聚合物.此外,对配体及配位聚合物的荧光进行了研究.     

Distorted square-based pyramidal and trigonal bipyramidal geometries in a mercury (II) coordination compound containing 2-(aminomethyl)pyridine ligand

The new complex of [Hg(2-AMPy)₂Cl]₂.HgCl₄ (1) was synthesized from the reaction of HgCl₂ with 2-(aminomethyl)pyridine (2-AMPy) in methanolic solution. Suitable crystal of compound 1 for diffraction experiment was obtained by slow evaporation from dimethyl sulfoxide. Resulted complex was characterized by infrared, elemental analysis, thermal analysis, and single crystal X-ray diffraction. In the cationic part of this compound, two five-coordinated mercury centers have two different geometries, including distorted square-based pyramidal geometry by the trigonality index, τ₅, of 0.23 and trigonal bipyramidal geometries by the trigonality index, τ₅, of 0.57.     

[ONSO]型Salen化合物的合成、单晶结构及金属离子识别

一些重金属离子即使在较低浓度时也会对环境、生物体产生毒性,所以研究痕量金属离子识别具有重大意义。荧光传感器由于具有选择性好、灵敏度高、成本低、实时响应等优点, 得到了广泛关注。以2,4-二叔丁基苯酚,3,5-二叔丁基水杨醛和邻氨基苯硫酚为原料合成了类Salen配体L1, 并用1H NMR,13C NMR,IR,元素分析及X射线单晶衍射等手段对其进行了表征。并通过自由挥发法得到了配体L1的单晶结构,实验表明L1是三斜晶、P-1空间群的一个空穴平面[ONSO]四配位环境。通过荧光光谱考察了类Salen配体与金属离子(Li+,Na+,K+,Cd2+,Cs+,Co2+,Cu2+,Hg2+,Mn2+,Ni2+,Zn2+,Ag+)的识别与配位性能。光谱滴定分析表明L1与Zn2+以1∶1的化学计量数配位。另外,L1与Zn2+结合后荧光显著增强,荧光检测限达到5.01×10-5 mol·L-1,而上述提到的其他常见金属离子不引起荧光光谱变化。结果表明L1是一个对检测Zn2+的选择性高,灵敏度强的荧光增强型探针。     

配体取代基对三羰基铼配合物光催化还原CO2的影响

设计并合成了四种联吡啶配体上共价修饰不同取代基的三羰基铼配合物fac-Re(L)(CO)₃Cl: 即取代基分别为甲基(Re-Me)、羧基(Re-Ac)、季铵盐(Re-Qa)以及咪唑盐(Re-Im)的铼配合物, 化合物的结构均经过核磁氢谱、质谱以及红外光谱的确认, 测定了四种配合物第一和第二还原电位. 分别以该系列铼配合物为催化剂和光敏剂、三乙醇胺为电子牺牲体构建了均相可见光催化还原CO₂体系, 配体上取代基对催化剂的催化效果有显著的影响, 催化活性Re-Qa> Re-Ac≈Re-Me> Re-Im. 不同实验条件下四种催化剂的吸收光谱随时间变化研究表明, 铼配合物的催化效果和其在催化过程中的失活速率密切相关, 其变化趋势与催化剂失活速率一致, 催化剂的失活发生在催化剂得到一个电子后的单电子还原态中间体(One-electron reduced species, OER). 瞬态吸收光谱检测到了催化过程中的OER的生成, 证实光催化还原CO₂过程通过生成OER中间体进行的.     

柔性二羧酸铜配合物的合成与晶体结构

通过液相扩散法合成了一个新的配位聚合物Cu(CBA) PY2 (H2O)(CBA为4-(3('-)羧丙酰胺基)苯甲酸阴离子,Py为吡啶),并对该化合物进行了元素分析、红外、热重、粉末X射线衍射表征,其结构由X射线单晶衍射确定.该化合物属于单斜晶系,空间群P2/c,晶胞参数:C21 H21CuN3O6,a=2.15208(12) nm,b =0.57071 (3) nm,c=1.72977(9) nm,α=90°,β=94.3200(10)°,y=90°,R1=0.0296,wR2 =0.0801.在该配合物中,柔性二羧酸配体4-(3('-)羧丙酰胺基)苯甲酸阴离子桥联相邻的Cu(Ⅱ)离子形成一维链状结构,相邻链之间通过N-H…O和O-H…O氢键连接起来形成二维层状结构,层与层之间通过C-H…O氢键扩展成三维超分子结构.     

Harnessing the Anti-Nociceptive Potential of NK2 and NK3 Ligands in the Design of New Multifunctional μ/δ-Opioid Agonist–Neurokinin Antagonist Peptidomimetics

Opioid agonists are well-established analgesics, widely prescribed for acute but also chronic pain. However, their efficiency comes with the price of drastically impacting side effects that are inherently linked to their prolonged use. To answer these liabilities, designed multiple ligands (DMLs) offer a promising strategy by co-targeting opioid and non-opioid signaling pathways involved in nociception. Despite being intimately linked to the Substance P (SP)/neurokinin 1 (NK1) system, which is broadly examined for pain treatment, the neurokinin receptors NK2 and NK3 have so far been neglected in such DMLs. Herein, a series of newly designed opioid agonist-NK2 or -NK3 antagonists is reported. A selection of reported peptidic, pseudo-peptidic, and non-peptide neurokinin NK2 and NK3 ligands were covalently linked to the peptidic μ-opioid selective pharmacophore Dmt-DALDA (H-Dmt-d-Arg-Phe-Lys-NH₂) and the dual μ/δ opioid agonist H-Dmt-d-Arg-Aba-βAla-NH₂ (KGOP01). Opioid binding assays unequivocally demonstrated that only hybrids SBL-OPNK-5, SBL-OPNK-7 and SBL-OPNK-9, bearing the KGOP01 scaffold, conserved nanomolar range μ-opioid receptor (MOR) affinity, and slightly reduced affinity for the δ-opioid receptor (DOR). Moreover, NK binding experiments proved that compounds SBL-OPNK-5, SBL-OPNK-7, and SBL-OPNK-9 exhibited (sub)nanomolar binding affinity for NK2 and NK3, opening promising opportunities for the design of next-generation opioid hybrids.     

Synthesis, Crystal Structure and Fluorescence Property of a Binuclear Zn(II) Complex: [Zn2(μ-N3)2(N3)2(L)2] [L?=?1-(1,10-phenanthrolin-2-yl)-2-pyridone]

Abstract  Hydrated zinc perchlorate reacted with sodium azide and 1-(1,10-phenanthrolin-2-yl)-2-pyridone (L) in methanol solution and resulted in the formation of a new binuclear complex: [Zn₂(μ-N₃)₂(N₃)₂(L)₂]. The complex has been characterized by elemental analysis and IR spectrum, and its crystal structure determined by X-ray crystallography and the complex crystallizes in the monoclinic system with space group P2₁/c and a = 11.409(2), b = 8.0733(15), c = 18.163(3) Ǻ, β = 99.095(3)°. In the complex two azide anions act as bridge ligand and another two azide anion and two 1-(1,10-phenanthrolin-2-yl)-2-pyridone function as terminal ligands, and Zn(II) ion lies in a distorted triangle bipyramid geometry. Index Abstract  The title binuclear Zn(II) complex was synthesized by zinc perchlorate, sodium azide and 1-(1,10-phenanthrolin-2-yl)-2-pyridone and its crystal structure determined. Single crystal X-ray diffraction analysis reveals that azide anion function as both bridge ligand and terminal ligand, and 1-(1,10-phenanthrolin-2-yl)-2-pyridone only acts as a terminal ligand.      

Crystal Structures of Energetic Compounds. I. Safe Small-Scale Preparation and X-Ray Structure Determination of the High-Energy Cobalt(III) Complex [Co(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>N<Subscript>3</Subscript>](N<Subscript>3</Subscript>)<Subscript>2</Subscript>

Abstract  Well-formed dark red single-crystals of the potentially explosive cobalt(III) azido complex [Co(NH₃)₅N₃](N₃)₂ (nitrogen content: 72.59%) have been grown using a safe small-scale preparation from [Co(NH₃)₅N₃]Cl₂ and sodium azide. The complex crystallizes in the orthorhombic system, space group Pnma with unit cell parameters a = 12.921(3) ?, b = 10.346(2) ?, c = 8.0315(16) ?, V = 1,073.7(4) ?³ and Z = 4. Five NH₃ ligands and the azide anion surround the Co³⁺ ion in a nearly perfect octahedral geometry. Two azide anions are non-coordinating, and no water of crystallization is present in the crystal structure. Graphical Abstract  Well-formed dark red single-crystals of the potentially explosive cobalt(III) azido complex [Co(NH₃)₅N₃](N₃)₂ (nitrogen content: 72.59%) have been grown using a safe small-scale preparation from [Co(NH₃)₅N₃]Cl₂ and sodium azide. Five NH₃ ligands and the azide anion surround the Co³⁺ ion in a nearly perfect octahedral geometry. Two azide anions are non-coordinating, and no water of crystallization is present in the crystal structure.      

基于一维[H_2Mo_4O_(14)]_n~(2n-)链和双吡啶双酰胺配体的三维锌配合物的合成、结构与性能

选择柔性的双吡啶双酰胺配体N,N'-双(3-吡啶甲酰胺基)-1,2-乙烷(3-bpye)、钼酸铵和氯化锌在水热条件下自组装制备了一个基于一维[H_2Mo_4O_(14)]_n~(2n-)链的三维锌配合物[Zn(3-bpye)(H_2Mo_4O_(14))(H_2O)_2],并通过元素分析、红外光谱、热重分析等技术手段研究了配合物的结构,并利用X射线单晶衍射分析进行了晶体结构表征。结构解析揭示标题配合物是三斜晶系,P-1空间群,晶胞参数a=0.61310(3)nm,b=1.04750(6)nm,c=1.06540(6)nm,α=78.5540(10)°,β=77.5350(10)°,γ=89.9050(10)°,V=0.65420(6)nm~3,M_r=981.47,D_c=2.491 g/cm~3,Z=1,F(000)=468,R_1=0.0290,ωR_2=0.1068。标题配合物中,金属锌离子连接一维[H_2Mo_4O_(14)]_n~(2n-)链形成一种二维无机双金属层[Zn(H_2Mo_4O_(14))]_n,相邻的层间又通过双齿配体3-bpye连接形成三维CdSO_4拓扑的骨架结构。配合物表现出强的荧光发射特性,而且其在紫外光照下对亚甲基蓝和罗丹明B均有明显的催化降解活性。