新型柱-层结构的金属有机配位聚合物的合成与性质

利用5-磺基间苯二甲酸单钠盐（NaH₂L）和La(NO₃)₃在水热条件下成功合成了一种新型配位聚合物[La(L)(H₂O)₃]_n·nH₂O（1, CCDC: 1422966）,其结构和性质经IR, X-射线单晶衍射,元素分析,热重分析和FL表征。结果表明：La³⁺为九配位,呈三帽三棱柱配位构型。化合物1基于La³⁺和L^3-配体的两种拓扑非等价节点,呈现出五连接3D柱层状金属有机骨架结构,Schlafli符号为(4⁵, 6⁵)。化合物¹的荧光发射峰位于410 nm,归属于配体到金属的电荷转移。     

多苯并咪唑锰( Ⅱ )配合物的合成及对DNA凝聚的促进作用

以多苯并咪唑配体1,1,4,7,7-五(2-苯并咪唑甲基)-二乙基三胺(DTPB)为主配体, 合成了锰(Ⅱ)配合物[Mn(DTPB)Ac]Ac·8H₂O(1)和[Mn₂(DTPB)(NO₃)₂(H₂O)₂][Mn₂(DTPB)(NO₃)₂(H₂O)(CH₃OH)]·(NO₃)₄·5CH₃OH·H₂O(2), 并对其进行了表征. 利用紫外-可见吸收光谱和黏度实验研究了配合物1和2与DNA的相互作用, 发现这2个配合物均能与DNA结合, 并对配合物与DNA作用的机理进行了探讨. 利用琼脂糖凝胶电泳和直角光散射(RALS)技术研究了配合物1和2促进DNA凝聚的性质. 结果表明, 在近中性条件下2个配合物都能促使DNA凝聚. 利用透射电子显微镜(TEM)观察了不同凝聚体的形态.     

氮氧杂链型配体合成与Cu(Ⅱ)和Zn(Ⅱ)配位性质研究

合成了4种氮氧杂链型配体N,N'-二-(2-羟乙基)-乙二胺(L¹)、N-(2-羟基苄基)-丙醇胺(HL²)、N-(2-羟乙基)-N'-(2-羟基苄基)-乙二胺(HL³)和N-(2-羟乙基)-二乙三胺-(L⁴),通过元素分析、IR和¹H NMR等手段表征了其结构,用pH电位滴定法在25℃、I=0.10(KNO₃)条件下,测定了L¹和HL²与Cu(Ⅱ)离子以及HL³和L⁴与Zn(Ⅱ)离子配位平衡常数.结果表明:L¹和HL²与Cu(Ⅱ)离子配位时,均可生成四配位配合物,其中第三配位点醇羟基配位较强,其质子离解常数pK_a1分别为7.28和7.32;第四配位点是第2个醇羟基或1个水分子配位,其pK_a2分别为9.33和9.04;HL³和L⁴与Zn(Ⅱ)均可生成五配位配合物,第四配位点均为醇羟基,其离解常数pK_a1分别为7.76和7.96,第五配位点均为H₂O,其pK_a2分别为9.47和9.57.从上述热力学结果可见,配合物在中性pH值范围能生成亲核试剂Cu(Ⅱ)…^-OR或Zn(Ⅱ)…^-OR,而且均具备双重催化酯类底物水解的条件.     

取代基对咪唑[4,5-f]-1,10-邻菲罗啉Ru(Ⅱ)配合物的温敏性能影响

合成了3种具有不同取代基的咪唑[4, 5-f]-1,10-邻菲罗啉配体L¹~L³及其Ru(Ⅱ)配合物[Ru(L¹)₃]、[Ru(L²)₃]和[Ru(L³)₃],并进行了表征。这些Ru(Ⅱ)配合物在溶液中具有π→π^*跃迁吸收峰和金属到配体的电荷转移跃迁(MLCT)吸收峰,其发光峰位约为590 nm左右。将Ru(Ⅱ)配合物掺杂到聚甲基丙烯酸甲酯(PMMA)中得到相应的温敏漆。Ru(Ⅱ)配合物在PMMA膜中的吸收峰精细结构消失,且在长波方向663 nm附近有新的发射峰,表明Ru(Ⅱ)配合物在PMMA膜中有聚集。温度升高后,Ru(Ⅱ)配合物在PMMA膜中的发射峰强度逐渐减弱。分别计算了在30~60 ℃和60~90 ℃区间内非辐射活化能E_nr和温度灵敏度S_T。结果表明,具有苯基取代的咪唑[4, 5-f]-1,10-邻菲罗啉配体的[Ru(L¹)₃]配合物,比咪唑[4, 5-f]-1,10-邻菲罗啉Ru(Ⅱ)配合物[Ru(L²)₃]及烷基取代基的咪唑[4, 5-f]-1,10-邻菲罗啉Ru(Ⅱ)配合物[Ru(L³)₃]具有更高的温度灵敏度。     

N,O-配体钴化合物的合成及其环氧丙烷羰化酯化的催化性能

合成了9种N,O-配体化合物L¹～L⁹.化合物L¹～L⁴分别与0.5 equiv.Co₂(CO)₈发生氧化还原配位反应生成中性单核钴化合物1～4;L⁵～L⁷分别与1 equiv.Co₂(CO)₈发生歧化和氧化还原配位反应;L⁸与5/6 equiv.Co₂(CO)₈以及1.2equiv.MeOH和0.4 equiv.H₂O发生歧化和氧化还原配位反应;L⁹与0.5 equiv.Co₂(CO)₈发生歧化配位反应生成同钴核离子对化合物5～9.这些化合物中的阴离子均为[Co(CO)₄]^-.相应地,化合物8中的阳离子是三核钴簇,其它化合物中的阳离子都是单核钴.化合物1～9通过FT-IR谱...     

Coordination-driven self-assembly of palladium(Ⅱ)-based metallacalixarenes as anion receptors using flexible pyridine-bridged diimidazole ligands

Two types of palladiu m(Ⅱ)-based metallacalixarenes[ML]²⁺and[ML₂]²⁺have been synthesized through coordination-driven self-assembly from a series of flexible pyridine-bridged diimidazole ligands[2,6-bis((1 H-imidazol-1-yl)methyl)pyridine(L¹),2,6-bis((1 H-benzo[d]imidazol-1-yl)methyl)pyridine(L²),2,6-bis((1 H-naphtho[2,3-d]imidazol-1-yl)methyl)pyridine(L³)],with palladium(II)-based building blocks[Pd(BF₄)₂(M¹-BF_4)and(tmeda)Pd(NO₃)₂(M²-NO₃)(tmeda=N,N,N',N'-tetramethyl-ethylenediamine)].All complexes were characterized by NMR spectroscopy(¹H NMR and¹³C NMR),mass spectrometry(CSIMS,ESI-HRMS)and elemental analysis.The single crystal X-ray diffraction analysis of[M¹L²_2](NO₃)₂,[M¹L³_2](NO₃)₂,[M¹L³_2](PF_6)_2 and[M~2 L³](NO₃)₂further confirmed the uniquely single bowl-shape and double bowl-shape structures.The anion binding properties within the metallacalixarenes as receptors were also investigated by NMR titration experiments in DMSO.     

新型苯并咪唑-5,6-二羧酸锌配合物的合成及其性能研究

以ZnSO₄·7H₂O和苯并咪唑-5,6-二羧酸为原料，采用水热法合成了一种新型的锌配合物{\[Zn(H₂-bidc)₂(H₂O)₄]·(H₂O)₄}_n[1 (CCDC: 1007038), H₃-bidc=苯并咪唑-5,6-羧酸]，产率48%，其结构经IR,元素分析和X-射线单晶衍射表征。结果表明：1属正交晶系，Pnnm空间群，晶胞参数a=9.6451(19) ， b=19.459(4) ， c=6.6895(13) ，α=β=γ=90°， V=1255.5(4) ³， Dc=1.634 g·cm^-3， Z=8。采用FL和TGA研究了1的性能。结果表明：1具有一定的热稳定性，最大发射峰位于420 nm和416 nm， 1的荧光发射属于发射配体荧光。     

2,2′-二甲基-4,4′-联苯二甲酸构筑的两个金属有机骨架

以2,2′-二甲基-4,4′-联苯二甲酸(H2L)为配体,采用溶剂热法合成了2个金属有机骨架:[Ni(μ₂-H₂O)(L)(DMF)(H₂O)]·0.5H₂O(1)和[Cd_2.5(L)(trz)₃(H₂O)₂]·2.5DMF(2)(DMF=N,N-二甲基甲酰胺,Htrz=1,2,4-三氮唑)。借助红外、热重、粉末和单晶X射线衍射对其进行了表征。单晶结构分析表明,1结晶于单斜晶系的P2₁/c空间群,镍离子处在拉长的[NiO₆]八面体中且分别被μ₂-H₂O和L^2-配体连接形成二维sql拓扑网络。2结晶于单斜晶系,C2/m空间群,含有3个不同的镉离子且均为扭曲的八面体构型。3个镉离子被三氮唑负离子以μ_1,2,4-桥连,在ab平面形成二维的kgd层,这些层再被L^2-配体沿c轴支撑形成(4,8)双节点的三维flu拓扑网络。热重分析表明,1和2的网络分别在390和230℃发生分解。     

基于2,6-二(4-羧基苯亚甲基)环己酮的金属-有机框架化合物的合成与表征

以2,6-二(4-羧基苯亚甲基)环己酮(H₂L)为配体得到一例锰金属-有机框架化合物[MnL]_n,并运用红外、热重、循环伏安、固体紫外、X射线光电子能谱和X射线单晶衍射对其进行表征。单晶衍射分析表明该配合物属于三斜晶系,空间群P1^-,不对称单元由Mn(Ⅱ)离子和一个L^2-配体组成。配体两端的羧基均为单齿配位,配体中间羰基上的氧参与配位,每个配体L^2-和3个Mn.离子配位,形成相对稳定的三角形配位构型。配合物中的Mn.与氧原子形成六配位构型,其中赤道面中的4个氧原子来自4个配体L^2-中单齿配位的羧基,上下顶点的2个氧原子分别来自配体L^2-中的羰基,从而形成八面体构型[MnO₆]。拓扑分析表明该金属-有机框架化合物具有二维kgd结构特征。循环伏安测试表明在扫速为30 mV·s^-1时,半波电位为171 mV,固体紫外光谱表明该化合物的带隙为1.76 eV。该化合物在染料分子如亚甲基蓝、甲基橙的降解过程中,具有一定的光催化活性。     

2-氯甲基苯并咪唑硝酸盐的晶体结构、质子化特征及量子化学理论研究

制备了2-氯甲基苯并咪唑硝酸盐(C₈H₈N₂Cl⁺·NO₃^-)化合物,采用元素分析,IR, ¹H NMR和TG-DTA对产物进行了表征,并采用X射线单晶衍射仪测定了该化合物的晶体结构,该化合物属单斜晶系,空间群P21/n, a=0.74189(3) nm, b=1.53064(6) nm, c=1.05478(3) nm, β=120.930(2)º, V=1.02744 nm³, D_c=1.484 g/cm³, Z=4, F(000)=472, μ=0.363 mm^-1, R=0.0659, wR=0.1498, GOF=0.840.在此基础上,采用量子化学方法,在MP2/6-311G^**, B3LYP/6-311G^**和HF/6-311G^**水平上计算了2-氯甲基苯并咪唑及其质子化阳离子的优化构型、电荷分布、振动光谱、热力学函数及总能量.计算结果显示2-氯甲基苯并咪唑环具有较强质子化能力,这与晶体结构结果相一致.     

Mononuclear, dinuclear, hexanuclear, and one-dimensional polymeric silver complexes having ligand-supported and unsupported argentophilic interactions stabilized by pincer-like 2,6-bis(5-pyrazolyl)pyridine ligands

The mononuclear complexes [Ag(H2L1)(Py)2](NO3) x H2O (1, H2L1 = 2,6-bis(5-methyl-1H-pyrazol-3-yl)pyridine) and [Ag(NO3)(L()] (2, L2 = 2,6-bis(5-methyl-1-isopropyl-1H-pyrazol-3-yl)pyridine), dinuclear complex [Ag2(H2L3)2(HL4)2] (3, H2L3 = 2,6-bis(5-phenyl-1H-pyrazol-3-yl)pyridine, HL4 = 6-(5-phenyl-1H-pyrazolyl-3-yl)picolinate), one-dimensional polymer {[Ag2(H2L1)2](NO3)2 x H2O}(n) (4), and hexanuclear clusters [Ag6(HL1)4](X)2 (X = NO3-, 5 ; BF4-, 6 ; ClO4-, 7) stabilized by pincer-like bispyrazolyl ligands have been prepared and characterized using (1)H NMR spectroscopy, elemental analysis, IR spectroscopy, luminescence spectroscopy and X-ray diffraction. In complex , there is a ligand unsupported Ag-Ag bond between the two silver atoms. Complex displays a one-dimensional polymer consisting of an infinite Ag-Ag chain and every two adjacent silver ions are bridged by an H2L1 ligand. Complexes and have the same Ag6 cores in which six silver atoms are held together by four HL1 and five Ag-Ag bonds, while complex was held together by six Ag-Ag bonds. The silver-silver distances in these complexes are found in the range of 2.874(1)-3.333(2) A for ligand supported, and 3.040(1) A for ligand unsupported Ag-Ag bonds, respectively. Complexes 3-7 are strongly luminescent due to either intraligand or metal-ligand charge transfer processes.     

Single-strand helical complexes constructed from 2-pyridinyl-3-pyridinylmethanone: tuning the helical pitch length by variation of metal cation and/or counter anion

The new ligand 2-pyridinyl-3-pyridinylmethanone (L) proves to be an excellent building block for the construction of single-strand helical architectures. A series of helical complexes have been synthesized by the reaction of L with various metal salts, in which L exhibits three kinds of coordination modes involving two kinds of bridging conformations, resulting in four types of single-strand helical chains. The counter anions in the series of 2(1) helical silver(I) complexes {[Ag(L)]X}(infinity)(X = NO(3), 1; PF(6), 2; BF(4), 3; ClO(4), 4; CF(3)CO(2), 5; CF(3)SO(3), 6) are fully or partially embedded inside the cylindrical helix, and the pitch length corresponds not only to the size of the anion but also to its manner of docking into the groove of the helix. Formation of the helical structure in {[Cu(L)(CH(3)CN)(H(2)O)(ClO(4))]ClO(4)}(infinity)(7) is driven by Ow-H...O (perchlorate) hydrogen bonding that leads to a stable triangular motif which rigidly fixes the configuration of the helix. In {[Co(L)(H(2)O)(3)](ClO(4))(2).2H(2)O}(infinity)(8) and {[Zn(L)(H(2)O)(3)](CF(3)SO(3))(2).H(2)O}(infinity)(9), similar helical chains without anion embedment suggest that the pitch length can be tuned by the size of metal cations. Notably, complex {[Ag(L)]CF(3)SO(3)}(infinity)(10), a conformational polymorph of , has a 4(1) helix induced by argentophilic interaction.     

Zinc(II) Complexes with 1H‐Imidazol‐4‐yl‐Containing Polyamine Ligand

The protonation and Zn^II/Cu^II complexation constants of tripodal polyamine ligand N¹‐(2‐aminoethyl)‐N¹‐(1H‐imidazol‐4‐ylmethyl)‐ethane‐1,2‐diamine (HL) were determined by potentiometric titration. Three new compounds, i.e. [H₃(HL)](ClO₄)₃ ( 5 ), [Zn(HL)Cl](ClO₄) ( 6 ) and {[Zn(L)](ClO₄)}_n ( 7 ) were obtained by reactions of HL · 4HCl with Zn(ClO₄)₂ · 6H₂O under different reaction pH, and they were compared with the corresponding Cu^II complexes reported previously. The results indicate that the reaction pH and metal ions have remarkable influence on the formation and structure of the complexes.     

两种异金属链状配位聚合物的合成和晶体结构

在甲醇溶液中,将K2NiL·H2O和M(OAC)2(M = Co,Zn)按1:1的摩尔比进行组装反应,得到了镍、钴和镍、锌两种异金属一维链状配位聚合物,其化学组成分别为{[Ni2Co2L2(H2O)2]·CH3OH·3H2O}n（1）和{[Ni2Zn2L2 (H2O)2]·2CH3OH·H2O}n（2）,（H4L=2-羟基-3-[(E)-({2-(2-羟基苯甲酰胺基)乙基}亚氨基)甲基]苯甲酸,OAC- = CH3COO-）。通过IR谱,元素分析的方法对其进行了表征,利用X-射线单晶衍射方法对其晶体结构进行了测定,结构分析表明：它们都是由不对称四核单元组成链状配位聚合物。     

异烟酰肼缩水杨醛Schiff碱配合物的合成与表征

采用直接合成法用异烟酰肼、水杨醛合成了异烟酰肼缩水杨醛Schiff碱,并以此为配体合成了Zn（Ⅱ）、Co（Ⅲ）、Ni（Ⅱ）的配合物．对配合物进行了元素分析,红外光谱,紫外光谱,差热-热重分析及摩尔电导的测试等表征,推测配合物的组成分别为[Zn（H2O）L],[Co（H2O）2（HL）2]NO3-H2O,[Ni（H2O）2HL]NO3,其中L=C13 H9O2N3．     

Distinct structures of coordination polymers incorporating flexible triazole-based ligand: topological diversities, crystal structures and property studies

Six new coordination polymers, namely {[Zn(btec)(0.5)(btmb)]·2H(2)O}(n) (1), {[Co(btec)(0.5)(btmb)(H(2)O)]·3H(2)O}(n) (2), {[Cu(btec)(0.5)(btmb)]·H(2)O}(n) (3), {[Cu(4)(btc)(4)(btmb)(4)]·H(2)O}(n) (4), {[Co(3)(bta)(2)(btmb)(2)]·2H(2)O}(n) (5), [Co(Hbta)(btmb)](n) (6) (H(4)btec = 1,2,4,5-benzenetetracarboxylate, H(3)btc = 1,3,5-benzenetricarboxylate, H(3)bta = 1,2,4-benzenetricarboxylate and btmb = 4,4'-bis(1,2,4-triazol-1-ylmethyl)biphenyl), have been successfully synthesized under hydrothermal conditions. All these complexes were structurally determined by single-crystal X-ray diffraction, elemental analysis, IR, TGA and XRD. Crystal structural analysis reveals that 1 is the first example of an unusual 3D framework with (8(6)) topology containing a 2D molecular fabric structure. Complex 2 exhibits a 3D NbO network with (6(4)·8(2)) topology. In 3, Cu(II) ions are coordinated by anti-conformational btmb ligands to form left- and right-handed double helices, which are further bridged by the 4-connected btec(4-) anions to give a 3D porous network. Complex 4 presents a rare 3D gra network structure with (6(3))(6(9)·8) topology. 5 and 6 were obtained through controllable pH values of solution, 5 features a scarce binodal (3,8)-connected tfz-d framework with the trinuclear Co(II) clusters acting as nodes, whereas 6 has an extended 2D 4(4) grid-like layer and the adjacent 2D layers are interconnected by strong hydrogen bonding interactions into a 3D supramolecular framework. The structural diversities indicate that distinct organic acid ligands, the nature of metal ions and the pH value play crucial roles in modulating the formation of the resulting coordination complexes and the connectivity of the ultimate topological nets. Moreover, magnetic susceptibility measurement of 5 indicates the presence of weak ferromagnetic interactions between the Co(II) ions bridged by carboxylate groups.     

Synthesis and Characterization of a New Symmetric Dinucleating Ligand and Its Dizinc(Ⅱ)Complex with Alkoxo and Carboxylate Bridges

<正>A novel dinuclear zinc(Ⅱ)complex[Zn_2L(μ-OAc)](PF_6)_2(CH_3OH)has been synthesized from a new symmetrical compartmental ligand HL in which the pendant arms,bearing pyridyl groups,are bridged by 1,3-diaminopropan-2-ol.X-ray crystal structure shows that the two zinc atoms reside within the adjacent ligand compartments and are bridged by the endogenous alkoxo-O from ligand and one exogenous carboxylate from acetate with a syn-syn mode.The coordination geometry of two zinc atoms is a distorted trigonal bipyramid with the pyridyl-N atoms and bridging alkoxo-O atom providing the equatorial donor set.Such coordination geometry observed in this complex is similar to that found in the dinuclear unit of phospholipase C.     

Anion control over interpenetration and framework topology in coordination networks based on homoleptic six-connected scandium nodes

Reaction of ScX3 (X=NO3-, CF3SO3-, ClO4-) with 4,4'-bipyridine-N,N'-dioxide (L) affords topologically distinct six-connected three-dimensional coordination frameworks, {[Sc(L)3](NO3)3}(infinity) (1), {[Sc(L)3](CF3)SO3)3(CH3OH)2.7(H2O)3}(infinity) (2), {[Sc(L)3](ClO4)3}(infinity) (3) and {[Sc(L)4(H2O)2](ClO4)3}(infinity) (4). Compounds 1, 2 and 3 are networks based on octahedrally co-ordinated ScO6 centres bound through six oxygen atoms from six separate N-oxide ligands L. Compounds 1 and 3 are doubly interpenetrated and have alpha-polonium-type structures of 4(12)6(3) topology based upon three intersecting (4,4) nets. The structure of 2 is unusual and shows parallel, co-planar layers of (4,4) nets connected in a criss-crossed fashion to afford a new 4(8)6(6)8 topology. In 4 only four ligands L bind to each Sc(III) centre with two additional water molecules bridging metal nodes. Significantly, the bridges formed by L do not sit in a plane and if connections through L are considered alone the resultant structure is a diamondoid array typically based upon a tetrahedral connecting node at Sc. Five interpenetrating diamondoid networks are observed that are cross-bridged by water molecules to form a single three-dimensional array of 4(8)6(7) topology. Compound 4 can also be viewed as incorporating two intersecting (4,4) grids based upon two ligands L and two bridging waters. Thus, variation of anion, solvent and conditions critically affects the structures of products formed, and the series of polymers reported herein illustrates how tectons based upon (4,4) grids can be combined and distorted to form non-NaCl topologies and even cross-bridged, multiply interpenetrated diamondoid materials. Both compounds 2 and 4 represent unusual examples of self-penetrated coordination frameworks.     

Homoleptic zinc(II) complexes with first and second coordination shells of 5-tert-butylpyrazole

Reaction of hydrated Zn[NO3]2 or Zn[BF4]2 with four or more equivalents of 3{5}-tert-butylpyrazole (L(tBu)) yields [Zn(L(tBu))4]X2 (X- = NO3- or BF4-). The nitrate complex contains C2-symmetric four-coordinate zinc(II) centers with a slightly flattened tetrahedral geometry, and each nitrate anion hydrogen bonds to two pyrazole N-H groups. Similar reactions with Zn[ClO4]2 or ZnCl2 in the presence of 2 equiv of AgPF6 or AgSbF6 yield instead [{Zn(L(tBu))4}(L(tBu))4][ClO4]2 and [{Zn(L(tBu))4}(L(tBu))2]Y2 (Y- = PF6- or SbF6-). Crystals of [{Zn(L(tBu))4}(L(tBu))4][ClO4]2 are composed of discrete [{Zn(L(tBu))4}(L(tBu))4]2+ supramolecules that are formed from N-H...N hydrogen bonding between zinc-bound and uncoordinated pyrazole rings. The [{Zn(L(tBu))4}(L(tBu))4]2+ moieties are linked into planar 4(4) nets by hydrogen bonding to bridging ClO4- anions. The ClO4- ions are almost perfectly encapsulated in near-spherical cavities of approximate dimensions 5.0 x 5.0 x 4.5 A that are formed by two interlocked supramolecular dications. Similarly, [{Zn(L(tBu))4}(L(tBu))2][PF6]2 crystallizes as discrete supramolecules in the crystal with the PF6- anions occupying a shallow bowl-shaped cavity on the surface of the complex that is formed by two zinc-bound and one uncoordinated pyrazole ligands. (1)H NMR and IR studies of [{Zn(L(tBu))4}(L(tBu))4][ClO4]2 in CD2Cl2 imply that the second-sphere L(tBu) ligands dissociate from the [Zn(L(tBu))4]2+ center in this solvent and that free and metal-bound L(tBu) are in rapid chemical exchange.     

Structures and magnetic properties of ferromagnetic coupling 2D Ln-M heterometallic coordination polymers (Ln = Ho, Er; M = Mn, Zn)

Four new heterometallic coordination polymers have been successfully synthesized, namely, {[Ho(2)(HCAM)(6)Mn(3)(H(2)O)(12)].17.5H(2)O}(n) (1), {[Er(2)(HCAM)(6)Mn(3)(H(2)O)(12)].17.5H(2)O}(n) (2), {[Ho(2)(HCAM)(6)Zn(3)(H(2)O)(12)].26H(2)O}(n) (3), and {[Er(2)(HCAM)(6)Zn(3)(H(2)O)(12)].26H(2)O}(n) (4) (H(3)CAM = chelidamic acid). X-ray crystallographic studies reveal that coordination polymers 1-4 are isostructural and crystallized in the rhombohedral crystal system, space group R3. These compounds comprise a 2D honeycomb-type framework. A 2D water sheet is first found in 3 and 4, which exhibits a novel topological motif. The magnetic results for 1-4 show that ferromagnetic interactions take place between the Ho(3+)/Er(3+) and Mn(2+) ions within 1 and 2.