基于柔性四羧酸配体构筑的两个镉(Ⅱ)配位聚合物的晶体结构及荧光性质（英文）

通过溶剂热和水热合成的方法制备了2个Cd(Ⅱ)配位聚合物[Cd_2(L)(DMF)_(1.5)(H_2O)_2]_n(1)和{[Cd(L)_(0.5)(4,4′-bpy)(H_2O)]·2H_2O}_n(2)(H_4L=5,5′-(己烷-1,6)-双-(氧基)-二-间苯二甲酸)。结构分析表明配合物1是一个(4,4)-连接的sql拓扑网络,拓扑符号为{4~4·6~2}_2。配合物2是一个(4,4,4)-连接的三重穿插的bbf网络,拓扑符号为(6~6)(6~4·8~2)。配合物1和2都呈现出较好的热稳定性和荧光性质。     

基于柔性四羧酸的三个一维/二维/三维Zn(Ⅱ)/Co(Ⅱ)配合物的晶体结构及荧光性质（英文）

通过水热/溶剂热合成的方法制备了3个Zn(Ⅱ)/Co(Ⅱ)配合物{[Zn(H_2L)(H_2O)_3]·H_2O·0.5H_4L}_n(1)、{[Co(L)_(0.5)(4,4'-bpy)]·0.5H_2O}_n(2)和{[Co(L)_(0.5)(pbmb)(H_2O)]·H_2O}(3)(H_4L=5,5'-(hexane-1,6-diyl)-bis(oxy)diisophthalic acid,4,4'-bpy=4,4'-bipyridine,pbmb=1,1'-(1,3-propane)bis-(2-methylbenzimidazole))。结构分析表明配合物1为一维链结构。2为拓扑符号为(6~4·7·8)(6·7~2)的三重穿插网络结构。3是拓扑符号为(4·6~2)(4~2·6~2·8~2)的(3,4)-连接的二维网络结构。配合物1呈现出较好的荧光性质。     

溶剂效应对金属有机骨架化合物结构的影响

以水和DMF为溶剂,在水热(溶剂热)条件下以"柱撑"方式利用相同的金属和配体合成了2个不同的新型金属有机骨架化合物[Cd(OBA)(bipy)]·DMF(1)和Cd(OBA)(bipy)(2)[OBA=4,4'-Oxybis(ben-zoic acid),bipy=4,4'-bipyridine].单晶X射线衍射分析数...     

两个3-氧乙酸基苯丙烯酸构筑的Cd(Ⅱ)配合物的合成、晶体结构和荧光性质(英文)

用水热法合成得到2个Cd(Ⅱ)配合物,[Cd(L)(4,4′-bipy)0.5(H2O)2]n(1)和[Cd(L)(bpp)(H2O)]n·2nH2O(2)(L=3-氧乙酸基苯丙烯酸,4,4′-bipy=4,4′-联吡啶,bpp=1,3-二吡啶基丙烷),并测定了他们的晶体结构。结构分析表明,在配合物1中,L配体连接Cd(Ⅱ)中心形成一维[CdL]n链,4,4′-联吡啶配体进一步桥联形成二维层状结构;配合物2是一个二重穿插的二维层状结构。此外,对配合物的荧光性能测试表明,它们在绿光区域有荧光发射。     

两个三维锌(Ⅱ)配位聚合物的晶体结构及荧光性质

通过水热合成的方法制备了2个Zn(Ⅱ)配位聚合物{[Zn_(1.5)(dbim)_(1.5)(btc)]·6H_2O}_n(1)和{[Zn(dbim)_(0.5)(btec)_(0.5)(H_2O)]·H_2O}_n(2)(dbim=1-(4-((2,6-dimethyl-2H-benzo[d]imidazol-3(3H)-yl)methyl)benzyl)-2,7-dihydro-2,5-dimethyl~(-1)H-benzo[d]imidazole,H_3btc=1,3,5-苯三酸,H_4btec=1,2,4,5-苯四甲酸)。结构分析表明配合物1是一个三节点(3,4,4)-连接的网络,拓扑符号为(5~2·6·7·8~2)(5~2·6)(5~2·6~2·8~2)。配合物2是一个(3,4)-连接的网络,拓扑符号为(8~3)(8~5·10)。配合物1和2的固态荧光与配体dbim不同。     

三角柔性多羧酸金属有机骨架化合物的合成、结构及荧光性质（英文）

以柔性1,3,5-三(4-羧酸苯氧基)苯(H3TCPB)为配体,以4,4′-联吡啶(4,4′-BPY)为辅助配体,在溶剂热条件下合成了2个新颖的分别具有三核锌簇和三核钴簇的金属有机骨架化合物:{[Zn3(TCPB)2(4,4′-BPY)]·DMF·3H2O}n(1)和{[Co1.5(TCPB)(DMF)(H2O)]·DMF}n(2),通过单晶X射线衍射,红外光谱,元素分析,热重分析和粉末X射线衍射对其结构进行了表征。单晶X射线衍射分析表明化合物1属于三斜晶系,P1空间群,表现出三维(3,8)连接的网状结构,拓扑符号为:{43}2·{46·618·84}·{6};化合物2也属于三斜晶系,P1空间群,为二维(3,6)连接的网络层状结构,拓扑符号为:{43}4·{46·618·84}。此外,荧光性质研究表明固态化合物1在室温条件下发射出源于TCPB3-和4,4′-BPY配体的淡蓝色荧光,而化合物2在相似的条件下没有荧光发射。     

3,5-二(吡啶-4-甲氧基)苯甲酸和芳香二羧酸配体构建的具有3,4-连接四重和三重穿插的d~(10)金属配位聚合物（英文）

以3,5-二(吡啶-4-甲氧基)苯甲酸(HL)与芳香二羧酸为配体,在水热条件下与Zn(Ⅱ)或Cd(Ⅱ)盐反应得到4个具有3,4-连接多重穿插结构的配位聚合物:[Zn_2L_2(tdc)]_n(1),{[Zn_4L_4(Hhdc)_2]·H_2O}n(2),{[Zn_2L_2(Hhdc)]·H_2O}n(3),{[Cd_2L_2(bdtc)(H_2O)]·0.5H_2O}n(4)(H_2tdc=2,5-噻吩二甲酸,H_3hdc=5-羟基间苯二甲酸,H_2bdtc=1,4-苯二硫乙酸)。晶体结构分析表明,聚合物1~3具有3,4-连接四重穿插的三维网络结构,拓扑符号分别为(4.82)(4.85)(1)、(63)(65.8)(2)和(63)(65.8)(3)。4为3,4-连接三重穿插的二维平面结构,拓扑符号为(6~3)(6~6)。测定了配位聚合物1、3和4的热稳定性和荧光性质。     

三个基于1,5-二(2-乙基苯并咪唑基)-戊烷柔性配体的镉配合物（英文）

通过设计柔性配体1,5-二(2-乙基苯并咪唑基)戊烷(bep),在二羧酸辅助配体的调控下成功制备了3个配位聚合物[Cd(bep)(sba)]_n(1),[Cd(bep)(bda)]_n(2),and{[Cd_2(bep)(ada)_2]·H_2O}_n(3)(H_2sba=4,4′-磺酰基二苯甲酸,H_2bda=4,4′-联苯二甲酸,H_2ada=1,3-金刚烷二乙酸)。配合物均呈现二维层状结构。配合物1由交替的Cd(Ⅱ)/bep/sba2-螺旋链构成。配合物2由Cd/bda2-单元构成二维结构,bep作为单齿配体与Cd(Ⅱ)配位。配合物3的二维层通过Cd/ada2-/H_2O氢键螺旋链拓展成三维超分子。此外,对配合物1~3的粉末X射线衍射、热稳定性以及荧光性质进行了研究。     

基于2-(4′-羧基苯基)咪唑-4,5-二羧酸构筑的三个镉/锌配位聚合物的合成、拓扑结构、荧光光谱及DNA作用（英文）

以2-(4′-羧基苯基)咪唑-4,5-二羧酸(H_4CPhIDC,C_(12)H_8N_2O_6)为配体,用溶剂热合成了3种配位聚合物{[Cd2(CPhIDC)(bimb)]·H_2O}_n(1)、{[Cd_2(CPhIDC)(phen)_2]·3H_2O}_n(2)、{[Zn_2(CPhIDC)(bpp)]·1.5H_2O}_n(3)(bimp=1,4-双咪唑基-丁烷,phen=1,10-菲咯啉,bpp=1,3-双(4-吡啶基)-丙烷)。用元素分析、红外光谱、粉末X射线衍射和单晶X射线衍射对配合物进行了表征和结构分析。结构分析表明,主配体以完全去质子化CPhIDC4-的形式与中心金属离子形成以μ_4和μ_5为配位模式的二维及三维聚合物。配合物1和3是三维网络结构,同时呈现(3,4,5)-连接的(5·6·7)(4·52·6·72)(4·52·6·74·82)拓扑结构,两者的不同之处是中心离子和辅助配体。配合物2是二维波纹状渔网结构,呈现44·62拓扑结构,在其空间填充上又类似于DNA双螺旋链的单螺旋结构。测定了产物的固体荧光光谱;用EtBr荧光探针法研究了配体及配合物与ct-DNA的相互作用。     

基于一种柔性双咪唑和不同双羧基配体构筑的两例镉(Ⅱ)的配位聚合物（英文）

在水热条件下合成了2个新颖的镉(Ⅱ)配位聚合物:[Cd_2(μ_2-H_2O)(1,5-Bip)(Tpa)_2]_n(1)和[Cd(1,5-Bip)(Oba)]_n(2)(H_2Oba=4,4′-二羧酸二苯甲醚,H_2Tpa=对苯二甲酸,1,5-Bip=1,5-二(咪唑基)戊烷)。并通过X射线单晶衍射,粉末XRD、红外光谱、元素分析以及热重分析对其结构进行表征。单晶解析结果表明:配位聚合物1是一个单节点5连接(4~6.6~4)拓扑三维空间网络结构,配位聚合物2是一个二维的(4,4)网格层状结构。另外,研究了2个配位聚合物在室温下的热稳定和荧光性能。     

Tuning Structural Topologies of Three Photoluminescent Metal-Organic Frameworks via Isomeric Biphenyldicarboxylates

Three new cadmium compounds, [Cd(2,4'-bpdc)(bib)(0.5)] (1; 2,4'-bpdc = biphenyl-2,4'-dicarboxylate and bib = 1,4-bis(2-methyl-imidazol-1-yl)butane), {[Cd(2)(3,4'-bpdc)(2)(bib)(1.5)(H(2)O)](n)·H(2)O}(n) (2; 3,4'-bpdc = biphenyl-3,4'-dicarboxylate), and [Cd (4,4'-bpdc)(bib)] (3; 4,4'-bpdc = biphenyl-4,4'-dicarboxylate), have been successfully synthesized by the assembly of Cd(2+) ions, bib ligands, and isomeric bpdc ligands, respectively. This paper presents a comparative study on the tuning of structural topologies using three isomers of biphenyldicarboxylates as bridging ligands. Compound 1 based on 2,4'-bpdc features a three-dimensional (3D) framework with 6-connected mab topology. Compound 2 based on 3,4'-bpdc is another 3D framework, but it possesses a rare 3-fold interpenetrating 4,6-connected fsh net, while compound 3 based on linear 4,4'-bpdc shows unusual 2D → 3D parallel polycatenation of (4,4) layers. Furthermore, the luminescent properties of three compounds are investigated in the solid state.     

An investigation of the self-assembly of neutral, interlaced, triple-stranded molecular braids

The synthesis and structures of six compounds prepared in two different systems have been explored with the purpose of isolating coordination polymers with interlaced triple-stranded molecular braid architectures. The dinuclear paddle-wheel units of [Cu(2)(maa)(4)2 H(2)O] can be rationally tuned to form three classes of isomorphous compounds, namely [Cu(2)(maa)(4)(bpp)] (1) (bpp=1,3-bis(4-pyridyl)propane, Hmaa=2-methylacrylic acid), [Cu(3)(maa)(6)(bpp)(2)] (2), and[Cu(4)(maa)(8)(bpp)(4)(H(2)O)(2)]2 H(2)O (3), with a bridging bpp ligand, at controlled ligand-to-metal molar ratios, and lead to three coordination polymers having similar one-dimensional characteristics but different mono- and dinuclear nodes. Compound 1, with a bpp:[Cu(2)(maa)(4)2 H(2)O] stoichiometry of 1:1, contains a zigzag chain containing dinuclear nodes, whereas polymer 2, with a bpp:[Cu(2)(maa)(4)2 H(2)O] stoichiometry of 1.5:1, also adopts the topology of a zigzag chain but with both mono- and dinuclear nodes. Compound 3, with a bpp:[Cu(2)(maa)(4)2 H(2)O] stoichiometry of 2:1, contains a neutral, interlaced, triple-stranded molecular braid, which is interwoven by three single-stranded meso-helical chains that contain only a mononuclear node. With the three aromatic chelating terminal ligands 2,2':6',2'-terpyridine (tpy), 1,10-phenanthroline (phen), and di(2-pyridyl)amine (dpa) we have also prepared three neutral complexes containing the linear, rigid bridging ligand biphenyl-4,4'-dicarboxylate (bpdc), namely [Cd(bpdc)(tpy)]H(2)O (4), [Cu(bpdc)(phen)(2)]4.25 H(2)O (5), and [Cu(bpdc)(dpa)] (6). An infinite meso-helix is formed initially in 4, and then three of these chains assemble into a triple-stranded braid similar to that of 3. Complexes 5 and 6 have a mononuclear and a looped dinuclear structure, respectively. Compounds 3 and 4 are unusual examples of triple-stranded molecular braid coordination frameworks based on different types of co-ligands.     

Syntheses,Hirshfeld surface analyses,and luminescence of four new complexes

Four Cd-based complexes with chemical formulae [Cd(L¹)₂(2,2'-Bipy)(H₂O)] (I), [Cd(L²)₂(2,2'-Bipy) · 2H₂O] (II), [Cd(L¹)₂(Phen)(H₂O)] (III), {[Cd(L¹)₂(H₂O)(4,4'-Bipy)] · 3H₂O} (IV) (HL¹ = 3-(4-hydroxyphenyl)propanoic acid, HL² = p-hydroxyphenylacetic acid, Phen = phenantroline), have been synthesized and structurally characterized (CIF file CCDC nos. 1044844 (I), 1044844 (II), 1044844 (III), 1044847 (IV)). Single-crystal X-ray analyses reveal that compounds I and III have mononuclear Cd(II) units linking by three carboxylate groups, complex II shows dinuclear motif, whereas IV exhibits 1D chain constructed by bridging 4,4'-Bipy ligand. The assistant effect of chelating N-donor ligands with 2,2'-Bipy and Phen bind and bridging 4,4'-Bipy, as well as the flexibility of carboxylate, play an important to modulate on the resulting motifs. The detailed analyses of Hirshfeld surface and fingerprint plots provide insight into the nature of non-covalent interactions in the title compounds. Furthermore, the luminescent properties of the all compounds were discussed in detail.     

含有微孔结构的吡啶二羧酸金属锰配位聚合物(英文)

<正>0 Introduction The realm of crystal engineering has provided a sound junction between aesthetics of crystalline architectures[1-2]and their potential functions[3-4],of which the ultimate destination is to successfully achieve     

Construction Of Two New 6‐connected Manganese(II) Metal Organic Frameworks via Isomeric Biphenyldicarboxylates Based on the Dinuclear Secondary Building Unit

Two coordination polymers, namely {[Mn(2,4′‐bpdc)(bimb)(H₂O)_0.5] · 0.5H₂O}_n ( 1 ) and [Mn(4,4′‐bpdc)(bimb)]_n · 2.5H₂O ( 2 ) [2,4′‐bpdc = biphenyl‐2,4′‐dicarboxylate, 4,4′‐bpdc = biphenyl‐4,4′‐dicarboxylate, and bimb = 1,4‐bis(1‐imidazol‐yl)‐2,5‐dimethyl benzene], were hydrothermally synthesized by reactions of manganese(II) salt with the rigid ligand 1,4‐bis(1‐imidazol‐yl)‐2,5‐dimethyl benzene and isomeric biphenyl dicarboxylate ligands. Complex 1 has an unusual 6‐connected three‐dimensional (3D) architecture with point symbol (4⁴.6¹¹). Complex 2 has also a 3D structure with two‐interpenetrated pcu topology with point symbol (4¹².6³). Structural comparisons show that the positions of the carboxylate groups in the ligand backbone play an important role in governing the structural topologies of these complexes.     

A 2-Fold Interpenetrated Framework Assembled from Pyridine-3-carboxylate Ligand and Transition Metal:Synthesis,Structure and Photoluminescent Property

A novel cadmium（Ⅱ） coordination polymer [Cd2（3-pa）4（4,4＇-bpy）（H2O）].3.08H2O 1 has been synthesized by pyridine-3-carboxylate （3-pall） and CdO with exo-bidentate rigid dipyridyl ligand 4,4＇-bipyridine （4,4＇-bpy） by using a hydrothermal method, its structure was determined by single-crystal X-ray diffraction and its luminescent property was also documented. Complex 1 crystallizes in orthorhombic space group Pbcn with a = 21.4074（14）, b = 27.1119（18）, c = 12.3879（8） A, V = 7189.9（8） A3, Z = 8, C34H32.16Cd2N6O12.08, Mr= 942.85, Dc = 1.742 g/cms, p = 1.255 mm-1 and F（000） = 3766. The structure was solved by direct methods and refined to R = 0.0353 and wR = 0.0891 for 6278 observed reflections （I 〉 2σ（I））. The most prominent structural feature is the mutual interpenetration of two identical 3-D open frameworks via filling the large void space, which gives a 2-fold interpenetrating architecture during the self-assembly process.     

Supramolecular Architectures with Open Frameworks Constructed by Transitional Metal Ions,Linear Dicarboxylic Acid,and 2,2′‐Bipyridine

Four new transitional metal supramolecular architectures, [Zn(cca)(2,2′‐bpy)]_n · n(2,2′‐bpy) ( 1 ), [Cu(cca)(2,2′‐bpy)]_n ( 2 ), [Zn(bpdc)(2,2′‐bpy)(H₂O)]_n · 0.5nDMF · 1.5nH₂O ( 3 ), and [Co(bpdc)(2,2′‐bpy)(H₂O)]_n · nH₂O ( 4 ) (H₂cca = p‐carboxycinnamic acid; H₂bpdc = 4,4′‐biphenyldicarboxylic acid; 2,2′‐bpy = 2,2′‐bipyridine) were synthesized by hydrothermal reactions and characterized by single crystal X‐ray diffraction, elemental analyses, and IR spectroscopy. Although the metal ions in these four compounds are bridged by linear dicarboxylic acid into 1D infinite chains, there are different π–π stacking interactions between the chains, which results in the formation of different 3D supramolecular networks. Compound 1 is of a 3D open‐framework with free 2,2′‐bpy molecules in the channels, whereas compound 2 is of a complicated 3D supramolecular network. Compounds 3 and 4 are isostructural. Both compounds have open‐frameworks.     

Self-assembly of 2D-->2D interpenetrating coordination polymers showing polyrotaxane- and polycatenane-like motifs: influence of various ligands on topological structural diversity

A series of mixed-ligand coordination complexes, namely, [Cd 2(bimb) 2(L (1)) 2] ( 1), [Cd(bpimb) 0.5(L (2))(H 2O)] ( 2), [Zn 5(bpib) 2(L (3)) 4(OH) 2(H 2O) 2] ( 3), [Zn(bpib) 0.5(L (4))] ( 4), and [Cd(bib)(L (4))] ( 5), where bimb = 1,4-bis((1 H-imidazol-1-yl)methyl)benzene, bpimb = 1,4-bis((2-(pyridin-2-yl)-1 H-imidazol-1-yl)methyl)benzene, bpib = 1,4-bis(2-(pyridin-2-yl)-1 H-imidazol-1-yl)butane, bib = 1,4-bis(1 H-imidazol-1-yl)butane, H 2L (1) = 4-((4-(dihydroxymethyl)phenoxy)methyl)benzoic acid, H 2L (2) = 4,4'-methylenebis(oxy)dibenzoic acid, H 2L (3) = 3,3'-methylenebis(oxy)dibenzoic acid, and H 2L (4) = 4,4'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))dibenzoic acid, have been synthesized under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric (TG) analyses. In 1, (L (1)) (2-) anions link the metal-neutral ligand subunits to generate a 2-fold parallel interpenetrating net with the 6 (3) topology. In 2- 4, neutral ligands connect the various metal-carboxylic ligand subunits to give a 2-fold parallel interpenetrating net with (4,4) topology in 2, a 2-fold parallel interpenetrating net with (3,6)-connected topology in 3, and a 3-fold parallel interpenetrating net with (4,4) topology in 4. Compounds 1- 4 display both polyrotaxane and polycatenane characters. Compound 5 is a 5-fold parallel interpenetrating net with (4,4) topology. By careful inspection of these structures, we find that different topological structures showing both polyrotaxane and polycatenane characters have been achieved with increase of the carboxylic ligand length. It is believed that various carboxylic ligands and N-donor ligands with different coordination modes and conformations are important for the formation of the different structures. In addition, the luminescent properties of these compounds are discussed.     

两个7-氧杂-二苯芴-3，11-二磺酸镉化合物的合成、结构与荧光性质研究(英)

通过使用浓硫酸对2，2′-二羟基-1，1′-二萘的磺化与成环反应得到一种新配体，7-氧杂-二苯芴-3，11-二磺酸。通过水热方法得到了它的两个化合物，[CdL(bipy)₂(H₂O)][Cd(bipy)₂(H₂O)₂]·L·H₂O (1)和[CdL(phen)₂(H₂O)]·5H₂O (2)，并通过X-射线单晶衍射分析进行结构表征。化合物1以P1空间群结晶，晶胞参数为a=1.205 5(6)，b=1.576 4(8)，c=1.954 5(10) nm，α=75.755(9)，β=88.093(10)，γ=89.035(10)°。化合物2以P2₁/ c空间群结晶，晶胞参数为a=2.104 0(7)，b=1.358 0(4)，c=1.428 9(5) nm，β=94.543(6)°。在化合物1中，有两个独立的镉(Ⅱ)离子不对称单元，在其中镉(1)离子和两个联吡啶上的四个氮原子，磺酸配体上的一个氧原子及一个水分子配位；镉(2)离子和两个联吡啶上的四个氮原子和两个水分子配位。两种固体化合物在室温下均显示强的蓝色荧光。     

由联苯二甲酸构筑的锌、镉配位聚合物的合成、结构及性质研究

用凝胶扩散法合成了2个新型的配位聚合物{[Zn(bpdc)(H2O)2].H2O}n(1)和[Cd(bpdc)(H2O)2]n(2)(H2bpdc=4,4′-联苯二甲酸)。X-射线单晶衍射分析表明配合物1属于单斜晶系,C2/c空间群,晶胞参数为a=0.693 66(11)nm,b=3.160 7(5)nm,c=0.626 80(9)nm,β=96.467°;配合物2属于正交晶系,Pnma空间群,晶胞参数为a=0.586 69(7)nm,b=2.914 1(4)nm,c=0.786 63(10)nm。热重分析和荧光光谱分析表明配合物1和2的热稳定性较好,与游离配体相比其荧光的发射波长发生红移而强度明显增强。