阴离子调控的含反式-双(苯甲酰丙酮)-1,4-环己二胺银配位聚合物的合成、晶体结构及其荧光性质

将配体反式-双(苯甲酰丙酮)-1,4-环己二胺(L)与AgX(X=NO₃^-,BF₄^-,SbF₆^-,ClO₄^-)进行反应得到4个配合物{[Ag(L)]NO₃}_n(1),{[Ag(L)(H₂O)]BF₄}_n(2),{[Ag₂(L)₃](SbF₆)₂}_n(3),{[Ag(L)]ClO₄}_n(4),并用元素分析,红外和X-射线单晶衍射表征了4个配合物的结构。在固体状态下,配合物1和2都形成2D网状结构的配位聚合物,都有2个不同配位类型的配体,不同的是,配合物1中桥连配体的1,4-环己二胺1,4位的C-N键在直立键上,而配合物2中桥连配体的1,4-环己二胺中1,4位的C-N键在平伏键上;配合物3也有2种不同配位类型的配体,但是与配合物1和2不同,配合物3形成1D配位聚合物;配合物4中的配体只有一种配位类型,配合物4形成2D网状结构。4个配合物中,配合物2,3的阴离子未参与Ag(Ⅰ)配位,配合物1和1的阴离子与Ag(Ⅰ)配位。同时,研究了配体和配合物在室温下的固态荧光性质。     

基于半夹心Cp*Rh单元的超分子桥环和螺环化合物的构筑策略

桥环和螺环化合物是有机化学中常用的概念而在其他领域鲜有提及。在本研究中,我们将桥环和螺环的概念拓展至超分子化学领域中并提出了相应的构筑策略。在刚性直线型配体中引入额外的螯合位点,通过配位驱动、分步组装的方法合成了复杂的3个有机金属超分子桥环化合物[(Cp*Rh)₆(μ-η²-η²-C₂O₄)₂(μ-C₂O₄)(L^A)₂](OTf)₆(1)、[(Cp*Rh)₆(dhbq)₂(pyrazine)(L^A)₂](OTf)₈(2)和[(Cp*Rh)₆(tpphz)₂(bpea)(L^A)₂](OTf)₁₂(3),以及一个超分子螺环化合物(Cp*Rh)₁₂(bibzim)₃Ru (L^A)₃(L^B)₃](OTf)₁₀(PF₆)₄(4),其中L^A=3,3′-di (pyridin-4-yl)-2,2′-bipyridine,OTf^-=CF₃SO^3-,dhbq=2,5-dihydroxy-1,4-benzoquinone,tpphz=tetrapyrido[3,2-a∶2′,3′-c∶3″,2″-h∶2'',3''-j]phenazine,bpea=1,2-di (pyridin-4-yl) ethane,bibzim=2,2′-bisbenzimidazole,L^B=4,4′-di (pyridin-4-yl)-1,1′-biphenyl。并通过单晶X射线衍射的方法一一表征了它们的单晶结构。     

Co(Ⅱ)与甜菜碱类衍生物形成的两种配合物的结构和磁性特征

合成了2种新的Co(Ⅱ)的配合物{[Co(L1)₂(H₂O)₂](ClO₄)₂·4H₂O}_n(1)和{[Co(L2)₂(H₂O)₄](ClO₄)₂·8H₂O·L2}_n(2)(L1=1,1'-(4,4'-二亚甲基联苯)二(1-吡啶鎓-3-羧酸盐),L2=1,1'-(4,4'-二亚甲基联苯)二(1-吡啶鎓-4-羧酸盐)),并且分别用红外光谱、热差分析、X射线粉末衍射和X射线单晶衍射表征了这两种化合物。晶体结构分析表明L1,L2,1和2分别属于P2₁/c,P2₁/c,P1和P1空间群。化合物1为二维的配位聚合物,2为单核配合物。二者的晶体结构都含有大量的氢键作用或者配位键形成的孔状结构。此外,磁性研究表明,1和2中都存在反铁磁性相互作用。     

Ag(Ⅰ)、Pd(Ⅱ)异核金属簇合物的制备和晶体结构研究

The complexes of [Ag₂Pd₂(μ-dppm)₂(μ-S₂CNC₄H₈)₂(μ₃-S₂CNC₄H₈)₂](SbF₆)₂·Et₂O (1) and [AgPd(S₂CN C₄H₈)(μ-dppm)₂](SbF₆)·H₂O (2)were synthesized and their single crystal structures were determined by X-ray diffraction. The complex 1 is monoclinic system, space group P2₁/c with a=1.14370(3)nm, b=1.39025(4)nm, c=2.93579(8)nm, β=95.173(1)°, V=4.6490(2)nm³, Z=4, D_c=1.716g·cm^-3, μ(Mo Kα)=1682cm^-1, F(000)=2384, M_r=2401.98, R=0.0662, wR=0.1302. The complex 2 is monoclinic system, space group Cc with a=2.74136(6)nm, b=1.04317(2)nm, c=2.523990(10)nm, β=95.173(1)°, V=4.6490(2)nm³, Z=4, D_c=1.716g·cm^-3, μ(Mo Kα)=1682cm^-1, F(000)=2384, M_r=2401.98, R=0.0662, wR=0.1302. CCDC: 1, 213613; 2, 213612.     

基于半夹心Cp*Rh单元的超分子桥环和螺环化合物的构筑策略

桥环和螺环化合物是有机化学中常用的概念而在其他领域鲜有提及。在本研究中,我们将桥环和螺环的概念拓展至超分子化学领域中并提出了相应的构筑策略。在刚性直线型配体中引入额外的螯合位点,通过配位驱动、分步组装的方法合成了复杂的3个有机金属超分子桥环化合物[(Cp*Rh)₆(μ-η²-η²-C₂O₄)₂(μ-C₂O₄)(L^A)₂](OTf)₆(1)、[(Cp*Rh)₆(dhbq)₂(pyrazine)(L^A)₂](OTf)₈(2)和[(Cp*Rh)₆(tpphz)₂(bpea)(L^A)₂](OTf)₁₂(3),以及一个超分子螺环化合物(Cp*Rh)₁₂(bibzim)₃Ru(L^A)₃(L^B)₃](OTf)₁₀(PF₆)₄(4),其中L^A=3,3''-di (pyridin-4-yl)-2,2''-bipyridine,OTf-=CF₃SO₃^-,dhbq=2,5-dihydroxy-1,4-benzoquinone,tpphz=tetrapyrido[3,2-a∶2'',3''-c∶3″,2″-h∶2‴,3‴-j]phenazine,bpea=1,2-di (pyridin-4-yl) ethane,bibzim=2,2''-bisbenzimidazole,L^B=4,4''-di (pyridin-4-yl)-1,1''-biphenyl。并通过单晶X射线衍射的方法一一表征了它们的单晶结构。     

金和银氮杂环卡宾原子簇化合物的合成结构与细胞毒性研究

由[Ag₃L₂(CH₃CN)₂](PF₆)₃(1,L=bis(N-pyridylimidazoliumyl)methane)通过金属转移反应合成了含有氮杂环卡宾配体的金银混合原子簇化合物,[Au₂AgL₂(CH₃CN)₂](PF₆)₃(2)和[Au₄AgL₄](PF₆)₅(3),用X-射线单晶衍射确定了2和3的晶体结构。化合物1和2结构相同,3个金属原子三角形排列。化合物3中5个金属原子呈链状排列,其中银原子居于中间。这些化合物在室温下分别在417,415和457 cm^-1处表现荧光。用MTT实验方法研究了对HuH7,C6和A375肿瘤细胞的毒性,其毒性顺序为1>2>3与这些化合物中银含量顺序相一致。     

两种含有十二元环的层状稀土硫酸盐的合成、结构表征及性质研究

通过溶剂热合成技术,我们得到了两种新的二维层状稀土硫酸盐:[Tb₂(SO₄)₅][(CH₃)₂NH₂]₄(1)和[Y₂(SO₄)₅][(CH₃)₂NH₂]₄(2),并通过X-射线衍射、元素分析及红外、热重对化合物进行了表征。两种化合物都属于三斜晶系,P1空间群。其中化合物1:a=0.9887(3)nm,b=1.1061(3)nm,c=1.5354(4)nm,α=70.45(0)°,β=75.12(0)°,γ=67.11(0)°,Z=2;化合物2:a=0.9816(5)nm,b=1.1001(5)nm,c=1.5286(8)nm,α=70.44(1)°,β=75.45(1)°,γ=67.48(1)°,Z=2。通过对晶体结构进行表征我们发现两种化合物都含有二维层状无机骨架结构,该层由2种不同类型的双链和十二元环构成。我们还对化合物1的荧光性质进行了研究,其在369nm的激发波长下表现出了Tb³⁺ 的特征发射。     

阴离子调控的含反式-双(苯甲酰丙酮)-1,4-环己二胺银配位聚合物的合成、晶体结构及其荧光性质

将配体反式-双(苯甲酰丙酮)-1,4-环己二胺(L)与AgX(X=NO₃^-, BF₄^-, SbF₆^-, ClO₄^-)进行反应得到4个配合物{[Ag(L)]NO₃}_n(1), {[Ag(L)(H₂O)]BF₄}_n(2), {[Ag₂(L)₃](SbF₆)₂}_n(3), {[Ag(L)]ClO₄}_n(4),并用元素分析,红外和X-射线单晶衍射表征了4个配合物的结构。在固体状态下,配合物1和2都形成2D网状结构的配位聚合物,都有2个不同配位类型的配体,不同的是,配合物1中桥连配体的1,4-环己二胺1,4位的C-N键在直立键上,而配合物2中桥连配体的1,4-环己二胺中1,4位的C-N键在平伏键上;配合物3也有2种不同配位类型的配体,但是与配合物1和2不同,配合物3形成1D配位聚合物;配合物4中的配体只有一种配位类型,配合物4形成2D网状结构。4个配合物中,配合物2,3的阴离子未参与Ag(Ⅰ)配位,配合物1和4的阴离子与Ag(Ⅰ)配位。同时,研究了配体和配合物在室温下的固态荧光性质。     

两种含有十二元环的层状稀土硫酸盐的合成、结构表征及性质研究

通过溶剂热合成技术,我们得到了两种新的二维层状稀土硫酸盐：[Tb₂(SO₄)₅][(CH₃)₂NH₂]₄(1)和[Y₂(SO₄)₅][(CH₃)₂NH₂]₄(2),并通过X-射线衍射、元素分析及红外、热重对化合物进行了表征。两种化合物都属于三斜晶系,P1空间群。其中化合物1：a=0.988 7(3) nm,b=1.106 1(3) nm,c=1.535 4(4) nm,α=70.45(4)°,β=75.12(3)°,γ=67.11(3)°,Z=2;化合物2：a=0.981 6(5) nm,b=1.100 1(5) nm,c=1.528 6(8) nm,α=70.44(6)°,β=75.45(6)°,γ=67.48(6)°,Z=2。通过对晶体结构进行表征我们发现两种化合物都含有二维层状无机骨架结构,该层由2种不同类型的双链和十二元环构成。我们还对化合物1的荧光性质进行了研究,其在369 nm的激发波长下表现出了Tb³⁺的特征发射。     

DDQ/PPh3催化的N-苯甲酰苯胺衍生物中间体的有效合成及晶体结构

在DDQ/PPh₃作用下,以2-异丙基苯甲酸或水杨酸为原料,在温和条件下以较高的收率合成、分离得到两个化合物(2)和(3)。化合物(2)和(3)与苯胺在氯仿中加热回流可分别转化为酰胺类化合物(4)和(5)。所有化合物通过元素分析、质谱、核磁共振进行了表征,并解析了化合物(2)和(3)的X-衍射单晶结构。化合物1,2-二(2-异丙基苯甲酸)-2,3-二氰-5,6-二氯苯(2)晶体属单斜晶系,空间群P2₁/c,其晶胞参数为：a=1.2875(3)nm,b=1.5186(2)nm,c=1.5726(3)nm,β=122.23(3)°,V=2.6010(1)nm³,D_c=1.331g·cm^-3,Z=4,F(000)=1080,R₁=0.0572,wR₂=0.1260;化合物1,2-二(2-羟基苯甲酸)-2,3-二氰-5,6-二氯苯(3)晶体属三斜晶系,空间群P1,其晶胞参数为：a=0.87776(16)nm,b=1.13111(15)nm,c=1.18639(17)nm,α=69.290(2)°,β=89.409(3)°,γ=67.878(2)°,V=1.0104(3)nm³,D_c=1.542g·cm^-3,Z=2,F(000)=476,R₁=0.0383,wR₂=0.0931。强π-π堆积作用和分子间氢键将化合物(2)和(3)组装成稳定的三维结构。     

Metal‐Carbene‐Templated Photochemistry in Solution: A Universal Route towards Cyclobutane Derivatives

A series of dicarbene‐bridged metallacycles [Ag₂( 1 )₂](PF₆)₂, [Ag₂( 2 )₂](BF₄)₂, [Ag₂( 3 )₂](PF₆)₂, [Ag₂( 7 )₂](BF₄)₂, [Ag₂( 8 )₂](BF₄)₂ and [Ag₂( 11 )₂](PF₆)₂ were obtained in high yields via the reactions of 1,2,4‐triazole‐, 1,2,3‐triazole‐ and imidazo[1,5‐a]pyridine‐based ligands with Ag₂O in CH₃CN. The C=C double bonds in all of the newly synthesized metallacycles went through [2 + 2] photodimerization under UV irradiation condition (λ = 365 nm, T = 298 K) yielding the dinuclear rctt‐cyclobutane‐silver(I) complexes [Ag₂( 4 )](PF₆)₂, [Ag₂( 5 )](BF₄)₂, [Ag₂( 6 )](PF₆)₂, [Ag₂( 9 )](BF₄)₂, [Ag₂( 10 )](BF₄)₂ and [Ag₂( 12 )](PF₆)₂, respectively with quantitative yields. Treatment of the these cyclobutane‐bridged silver(I) complexes with NH₄Cl resulted in the exclusive formation of cyclobutane derivatives after removal of the silver(I) metal ions.     

Synthesis, structural characterization, and luminescence properties of multinuclear silver complexes of pyrazole-functionalized NHC ligands containing Ag-Ag and Ag-π interactions

A few pyrazole-functionalized imidazolium salts have been prepared via the reactions of N-alkylimidazole and 3,5-bis(chloromethyl)pyrazole or 2-(1-(2-chloroethyl)-5-methyl-1H-pyrazol-3-yl)-6-(5-methyl-1-vinyl-1H-pyrazol-3-yl) pyridine. Reactions of these imidazolium salts with Ag₂O led to the successful isolation of tetranuclear [Ag₄(L)₂](X)₂ (X = PF₆⁻ or BF₄⁻; H₃L1 = 3,5-bis(N-benzylimidazoliumyl)pyrazole, H₃L2 = 3,5-bis(N-(2,4,6-trimethylphenyl)imidazoliumyl)pyrazole, H₃L3 = imidazolium cyclophane from the condensation of 3,5-bis(chloromethyl)pyrazole and 1,4-bis(imidazolyl)butane) and trinuclear silver clusters supported by N-heterocyclic carbene ligands in high yields. The molecular structures of these silver complexes have been confirmed by ¹H, ¹³C NMR, ESI-MS spectroscopy, and X-ray diffraction analyses. The tetranuclear complexes [Ag₄(L1)₂](PF₆)₂ (1) and [Ag₄(L2)₂](BF₄)₂ (2) consist of a pair of Ag-Ag contacts (ca. 3.11 Å) showing weak silver-silver interaction. [Ag₄(L3)₂](PF₆)₂ (3) has a square planar Ag₄ core sandwiched by two NHC cyclophanes with Ag-Ag distances of 3.22 Å. All the silver atoms in 1-3 are located in the same linear C-Ag-N coordination environment. [Ag₃(L4)₂] (PF₆)₃ (HL4 = 2-(1-(2-methylimidazoliumylethyl)-5-methyl-1H-pyrazol-3-yl)-6-(5-methyl-1-vinyl-1H-pyrazol-3-yl) pyridine) (4) is a trinuclear complex in which the three silver are bridged by two L4 molecules, and the Ag₃ units form one-dimensional chain via Ag-π interaction. The luminescence properties of the imidazolium salts and their silver complexes were also studied.     

Synthesis,crystal structure,fluorescence and electrochemical properties of two Ag(I) complexes based on 2-(4′-pyridyl)-benzoxazole/SPPh3 ligands

Abstract

To explore the luminescence properties of silver complexes in the solid state, two Ag(I) complexes, [Ag(4-PBO)₂(NO₃)] {di[2-(4′-pyridyl)-benzoxazole]silver(I) nitrate} (1) and [Ag₂(SPPh₃)₄](ClO₄)₂ {[tetra(triphenylphosphine sulfide)disilver(I)] diperchlorate} (2) (4-PBO =2-(4′-pyridyl)-benzoxazole, SPPh₃?=?triphenylphosphine sulfide), have been synthesized and characterized by elemental analysis, FT-IR and UV-Vis spectroscopy. Single-crystal X-ray diffraction revealed that 1 is three-coordinate by two nitrogen atoms from two 4-PBO ligands and an oxygen atom from the coordinated nitrate anion forming a triangular plane configuration. In 2, the SPPh₃ ligands adopt a monodentate coordinated and monoatomic bridging mode to connect two Ag(I) ions, resulting in a three-coordinate symmetrical binuclear structure. In the solid state, the luminescence properties of the ligands 4-PBO, SPPh₃ and their complexes were investigated. The results demonstrated that 1 results in the fluorescence quenching of aggregates due to the strong π–π stacking effect. The fluorescence enhancement of 2 may be attributed to the “aggregation-induced emission” (AIE) effect of restricted intramolecular rotations of the peripheral phenyl rings against the central core. In addition, cyclic voltammograms of 1 and 2 indicated an irreversible Ag⁺/Ag couple.     

Coordination modes of diphosphines in silver(I)–diphosphine complexes mediated by 2,4,6-tri(2-pyridyl)-1,3,5-triazine (tptz)

Silver (I) complexes [Ag₂(tptz)(dppm)₂(DMF)](BF₄)₂·2DMF (1), [Ag(tptz)(dppe)]_n(BF₄)_n·2nH₂O·nMeOH (2), [Ag₂(tptz)₂(dppp)₂](BF₄)₂ (3) and [Ag₂(tptz)₂(dppb)](BF₄)₂ (4) were obtained from the reactions of AgBF₄ and diphosphine Ph₂P(CH₂) _nPPh₂ (L_pp, n=1–4) in the presence of 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) in MeOH–DMF. Single crystal analyses showed that the closed metallocyclic unit [Ag₂(L_pp)₂]²⁺ with double L_pp bridges was obtained in (1) and (3) with an odd number of n, while an open metallochain (Ag₂L_pp)²⁺ with a single bridge formed in (2) and (4) with n being even. Coordination modes for the diphosphines are directly related to the rigid tptz ligand with a large -system.     

Synthesis,Characterization, and Properties of Organometallic Molecular Cylinders Bearing Bulky Imidazo[1,5-a]pyridine-Based N-Heterocyclic Carbene Ligands

The metal-controlled self-assembly of organometallic molecular cylinders from a series of imidazo[1,5-a]pyridine-based tris-NHC ligands is described in this report. The imidazo[1,5-a]pyridinium salts H₃- L (PF₆)₃ ( L = 4 a – 4 c ) were treated with 1.5 equivalents of Ag₂O to yield the trinuclear Ag^I hexacarbene cages [Ag₃( L )₂](PF₆)₃ ( L = 4 a – 4 c ), in which three Ag^I are sandwiched between the two tricarbene ligands. The silver(I) complexes [Ag₃( L )₂](PF₆)₃ underwent a facile transmetalation reaction in the presence of 3 equivalents of [AuCl(tht)] (tht=tetrahydrothiophene) to furnish the trinuclear Au^I cylinder-like cages [Au₃( L )₂](PF₆)₃ ( L = 4 a – 4 c ) without destruction of the metallosupramolecular structure. The new hexacarbene assemblies feature a large cavity that can easily accommodate a molecule of dimethyl sulfoxide as molecular guest. This is the first study of a unique “host–guest” system containing an organometallic cylinder-like cage derived exclusively from poly-NHC ligands.     

Design and characterization of silver(I) azide coordination polymers based on 1,2-bis(4-pyridyl)ethane and phenazine

Two silver(I) azide supramolecular coordination polymers (SCPs) with N-donor ligands have been synthesized and structurally characterized by physicochemical and spectroscopic methods; [AgN₃.bpe] where bpe = 1,2-bis(4-pyridyl)ethane, 1, and [(AgN₃)₂.phenz], 2, where phenz = phenazine. Syntheses were carried out in H₂O/acetonitrile/NH₃ media at room temperature. The topology of the bipodal ligands directs the silver azide building blocks to adopt different structures; 1D-chain, 1, or 1D-ribbon, 2. The azide groups exhibit an unusual bent structure with increasing bridging capability to adopt enough space for the bipodal ligands. The structure of SCP 2 contains the cyclic motif {Ag₂(μ₃-N₃)₂} to accommodate the voluminous phenz ligand. The emission spectra of the SCPs 1 and 2 display emission bands at 400–650 nm.     

C3‐Symmetric Assemblies from Trigonal Polycarbene Ligands and MI Ions for the Synthesis of Three‐Dimensional Polyimidazolium Cations

Metallosupramolecular poly‐NHC‐metal assemblies were prepared from trigonal hexakis (H₆‐ 1 a (PF₆)₆ and H₆‐ 1 b (PF₆)₆) or nonakis (H₉‐ 3 (BF₄)₉) imidazolium salts and Ag₂O. Complexes [Ag₆( 1 a )₂](PF₆)₆ and [Ag₆( 1 b )₂](PF₆)₆ are built from six Ag⁺ ions sandwiched between two trigonal hexacarbene ligands with an inner and an outer NHC donor in each of the three ligand arms. The metal atoms are arranged in two triangles. The hexakis‐NHC ligands bear cinnamic ester groups at the outlying NHC donors, used in postsynthetic [2+2] cycloaddition reactions linking two hexakis‐NHC ligands by three cyclobutane units to give complexes [Ag₆( 2 a )](PF₆)₆ and [Ag₆( 2 b )](PF₆)₆ bearing a dodecacarbene ligand. From the related nonakisimidazolium salt H₉‐ 3 (BF₄)₉, complex [Ag₉( 4 )](BF₄)₉ bearing an octadecacarbene ligand was obtained. Removal of the template metals yielded very large, stable, polyimidazolium cations with 12 or 18 internal imidazolium groups.     

Bis(μ-2-cyano­pyridine-N:N′)­bis­[(2-cyano­pyridine-N)silver(I)] bis­(tetra­fluoro­borate): an anion-linked molecular ladder

In the title compound, [Ag₂(C₆H₄N₂)₄](BF₄)₂, the Ag^I cations adopt distorted trigonal-planar coordination geometries. The Ag^I centres are linked via two bridging 2-cyano­pyridine ligands to give a centrosymmetric dinuclear complex in which the Ag^I coordination environment is completed by monodentate non-bridging 2-cyano­pyridine ligands. Bridging Ag⋯F(BF₂)F⋯Ag interactions link the dinuclear cations into molecular ladders.     

Synthesis and crystal structures of silver(I) and copper(II) complexes with <Emphasis Type="Italic">p</Emphasis>-xylylene-bridged bipyrazolyl ligands

Two semi-rigid bipyrazolyl ligands, namely 2,3,5,6-tetramethyl-1,4-bis[(3′,5′-dimethyl-1H -pyrazol-4′-yl)methylene]benzene (H₂L) and 2,3,5,6-tetramethyl-1,4-bis[(3′,5′-diphenyl-1H -pyrazol-4′-yl)methylene]benzene (H₂L′), and their Ag(I) and Cu(II) complexes have been prepared and structurally characterized by means of X-ray analysis. In the structures of the metal complexes, namely [Ag₂(H₂L)₂](BF₄)₂·2H₂O (1), [Ag(H₂L)(NO₃)]_n (2), [Cu₂(H₂L)₄(SO₄)₂]·11H₂O (3), and {[Ag(H₂L′)]BF₄}_n (4), the bipyrazoles act as bridging ligands to connect two metal atoms. Complexes 2 and 4 exhibit 1-D polymeric structures, while 1 and 3 are discrete molecules with a rectangular dimer or tetragonal prismatic shapes, respectively. Two different conformations, namely cis and trans, have been observed for these bipyrazolyl ligands.     

Introduction of secondary pyridyl-1H-tetrazole derivatives into Keggin–Ag–(1,10-phenanthroline) system for tuning dimensionalities and architectures: assembly and properties

By introducing three pyridyl-1H-tetrazole derivatives to Keggin–Ag-(1,10-phenanthroline) system, five new polyoxometalate-based inorganic–organic hybrid compounds with different dimensionalities and structures, [Ag₃(4-ptz)₂Na(phen)(HPMo₁₂O₄₀)]·2H₂O (1), [Ag₄(3-ptz)₂(phen)₂(HPMo₁₂O₄₀)] (2), [Ag₄(3-ptz)₂(phen)₂(HVW₁₂O₄₀)] (3), [Ag₃(3-bptzb)(phen)₂(PMo₁₂O₄₀)] (4) and [Ag₃(3-bptzb)(phen)₂(VW₁₂O₄₀)] (5) (phen = 1,10-phenanthroline, x-ptzH = 5-(x-pyridyl)-1H-tetrazole (x = 3, 4), 3-bptzb = 1,4-bis(5-(3-pyridyl)-tetrazolyl)butane), have been synthesized under hydrothermal conditions. Compound 1 is a 1-D belt architecture constructed from an Ag-4-ptz metal–organic chain and two Ag–PMo₁₂O₄₀–Na–phen inorganic–organic chains. When 3-ptzH was introduced as secondary ligand in 2 and 3 instead of 4-ptzH, two isostructural architectures were obtained, which contain a 1-D zigzag Ag-3-ptz chain with phen ligands hanging on both sides of the chain. The Keggin anions connect adjacent Ag-3-ptz chains to construct 2-D networks. When the flexible 3-bptzb was selected, isostructural 4 and 5 with 2-D networks were obtained, which were constructed from binuclear subunits and Keggin–Ag inorganic chains. The influence of three pyridyl-1H-tetrazole derivatives as secondary ligands on the dimensionalities and architectures of 1–5 was discussed. The electrochemical and photocatalytic properties of the compounds were investigated.