Silver(I) complexes in coordination supramolecular system with bulky acridine-based ligands: syntheses, crystal structures, and theoretical investigations on C-H...Ag close interaction

In our efforts to investigate the coordination architectures of transition metals and organic ligands with tailored structures, we have prepared two structurally related rigid bulky acridine-based ligands, 9-[3-(2-pyridyl)pyrazol-1-yl]- acridine (L(1)) and 9-(1-imidazolyl)acridine (L2), and synthesized and characterized four of their Ag(I) complexes, {[AgL1](ClO4)}2 (1), {[AgL1](NO3)}2 (2), [AgL2(2)](ClO4) (3), and {[(Ag3L2(3))(NO3)](NO3)2(H2O)}(infinity) (4). The single-crystal X-ray diffraction analysis shows that the structures of 1 and 2 are similar to each other, with the two intramolecular Ag(I) centers of each complex being encircled by two L1 ligands; this forms a unique boxlike cyclic dimer, which is further linked to form one-dimensional (1D) chains of 1 and a two-dimensional (2D) network of 2 by intermolecular face-to-face pi...pi stacking and/or weak C-H...O hydrogen-bonding interactions, respectively. 3 has a mononuclear structure, which is further assembled into a 2D network via intermolecular Ag...O and pi...pi stacking weak interactions. 4 possesses two different 1D motifs that are further interlinked through interlayer face-to-face pi...pi stacking and Ag...O weak interactions, resulting in a 2D network. It is worth noting that one of the interesting structural features of 1, 2, and 4 is the presence of obvious C-H...M hydrogen-bonding interactions between the Ag centers and some acridine ring H atoms identified by X-ray diffraction on the basis of the van der Waals radii. Furthermore, as a representative example, full geometry optimization on the basis of the experimental structure, the natural bond orbital (NBO), and topological analysis of 1 were carried out by DFT and AIM (Atoms in Molecules) calculations. The total C-H...Ag interaction energy in 1 is estimated to be about 14 kJ/mol. Therefore, this work offers three new rare examples (1, 2, and 4) that exhibit C-H...Ag weak interactions, in which the N donors of the acridine rings coordinate to Ag(I) ions. Also, these results strongly support the existence of C-H...Ag close interactions and allow us to have a better understanding of the nature of such interactions in the coordination supramolecular systems.     

Novel 2,7-substituted pyrene derivatives: syntheses, solid-state structures, and properties

A novel series of pyrene derivatives 3-6 functionalized with different aromatic substituents at 2,7-positions of the pyrene core have been readily synthesized by Suzuki coupling reactions. Single crystals suitable for X-ray crystallographic analysis of compounds 3-6 were all successfully obtained. The optical, electrochemical, and thermal properties of these newly synthesized compounds were thoroughly investigated and discussed. Theoretical calculation was adopted to study the geometric and electronic structure of compounds 3-6. Additionally, preliminary studies demonstrated that field-effect transistors using compound 3, 5, and 6 performed as p-type semiconductors, in which a field-effect mobility as high as 0.018 cm² V⁻¹ s⁻¹ and current on/off ratio of 10⁶ were achieved from compound 6.     

Two new coordination polymers constructed by angular tripyridyl ligand: syntheses,structures, and properties

U-shaped tripyridyl ligand 2,6-bis(pyridine-4-carboxamido)pyridine (L) was synthesized and used to assemble metal complexes. The resulting new complexes [Mn(L)₃(SCN)₂] _n (1) and [Co(L)₃(SCN)₂] _n (2) are isostructural, crystallizing in the monoclinic C2/c space group. In compounds 1 and 2, each metal is in a slightly distorted octahedron ligated by six nitrogens from four L and two SCN^?. Complexes 1 and 2 possess infinite 1-D zigzag polymeric chain structures where L adopts bridge and terminal coordination. These 1-D coordination polymers assemble into 3-D supermolecules of compounds 1 and 2 through hydrogen bonds. Fluorescence measurements and thermal analysis show that 1 emits strong fluorescence with a single broad band centered at 410?nm upon excitation at 357?nm and the polymeric chain structure is stable up to 340°C.     

Copper-bispidine coordination chemistry: syntheses,structures, solution properties,and oxygenation reactivity

Copper(I) and copper(II) complexes of two mononucleating and four dinucleating tetradentate ligands with a bispidine backbone (2,4-substituted (2-pyridyl or 4-methyl-2-pyridyl) 3,7-diazabicyclo[3.3.1]nonanone) have been prepared and analyzed structurally, spectroscopically, and electrochemically. The structures of the copper chromophores are square pyramidal, except for two copper(I) compounds which are four-coordinate with one noncoordinated pyridine. The other copper(I) structures have the two pyridine donors, the co-ligand (NCCH(3)), and one of the tertiary amines (N3) in-plane with the copper center and the other amine (N7) coordinated axially (Cu-N3 > Cu-N7, approximately 2.25 A vs 2.20 A). The copper(II) compounds with pyridine donors have a similar structure, but the axial amine has a weaker bond to the copper(II) center (Cu-N3 < Cu-N7, approximately 2.03 A vs 2.30 A). The structures with methylated pyridine donors are also square pyramidal with the co-ligands (Cl(-) or NCCH(3)) in-plane. With NCCH(3) the same structural type as for the other copper(II) complexes is observed, and with the bulkier Cl(-) the co-ligand is trans to N7, leading to a square pyramidal structure with the pyridine donors rotated out of the basal plane and only a small difference between axial and in-plane amines (2.15, 2.12 A). These structural differences, enforced by the rigid bispidine backbone, lead to large variations in spectroscopic and electrochemical properties and reactivities. Oxygenation of the copper(I) complexes with pyridine-substituted bispidine ligands leads to relatively stable mu-peroxo-dicopper(II) complexes; with a preorganization of the dicopper chromophores, by linking the two donor sets, these peroxo compounds are stable at room temperature for up to 1 h. The stabilization of the peroxo complexes is to a large extent attributed to the square pyramidal coordination geometry with the substrate bound in the basal plane, a structural motif enforced by the rigid bispidine backbone. The stabilities and structural properties are also seen to correlate with the spectroscopic (UV-vis and Raman) and electrochemical properties.     

Transition metal coordination complexes based on V-shaped bis-triazole ligand: syntheses,structures, and properties

Hydrothermal reactions of 1,3-bis(1,2,4-triazol-1-yl)benzene (btb) and M(NO₃)₂ (M = Co²⁺ (1), Cu²⁺ (2)) afforded two new coordination polymers, [Co(btb)₂(NO₃)(H₂O)]_n·NO₃·H₂O (1) and [Cu(btb)₂(NO₃)₂]_n (2), respectively. Single-crystal X-ray diffraction reveals that 1 crystallizes in the space group P2₁/m and 2 crystallizes in the space group Pī, both showing a double-stranded chain structure. The 1-D chains are interconnected via π?π interactions to lead to 2-D ladder-like supramolecular architectures. In addition, magnetic behavior and thermal stability of 1 and 2 have been investigated. For 1, weak antiferromagnetic interactions are observed at low temperature, and the data obey the Curie–Weiss law χ_M = C/(T?θ), with C = 3.22 cm³·mol^?1·K and θ = ?10.39 K. For 2, the decrease of the χT vs. T curve at low temperature is the result of intermolecular antiferromagnetic magnetic interactions.     

Regulation of geometry around the ruthenium center of bis(2-pyridinecarboxylato) complexes by the nitrosyl moiety: syntheses, structures, and theoretical studies

cis-[Ru(NO)Cl(pyca)(2)] (pyca = 2-pyridinecarboxylato), in which the two pyridyl nitrogen atoms of the two pyca ligands coordinate at the trans position to each other and the two carboxylic oxygen atoms at the trans position to the nitrosyl ligand and the chloro ligand, respectively (type I shown as in Chart 1), reacted with NaOCH(3) to generate cis-[Ru(NO)(OCH(3))(pyca)(2)] (type I). The geometry of this complex was confirmed to be the same as the starting complex by X-ray crystallography: C(13.5)H(13)N(3)O(6.5)Ru; monoclinic, P2(1)/n; a = 8.120(1), b = 16.650(1), c = 11.510(1) A; beta = 99.07(1) degrees; V = 1536.7(2) A(3); Z = 4. The cis-trans geometrical change reaction occurred in the reactions of cis-[Ru(NO)(OCH(3))(pyca)(2)] (type I) in water and alcohol (ROH, R = CH(3), C(2)H(5)) to form [[trans-Ru(NO)(pyca)(2)](2)(H(3)O(2))](+) (type V) and trans-[Ru(NO)(OR)(pyca)(2)] (type V). The reactions of the trans-form complexes, trans-[Ru(NO)(H(2)O)(pyca)(2)](+) (type V) and trans-[Ru(NO)(OCH(3))(pyca)(2)] (type V), with Cl(-) in hydrochloric acid solution afforded the cis-form complex, cis-[Ru(NO)Cl(pyca)(2)] (type I). The favorable geometry of [Ru(NO)X(pyca)(2)](n)(+) depended on the nature of the coexisting ligand X. This conclusion was confirmed by theoretical, synthetic, and structural studies. The mono-pyca-containing nitrosylruthenium complex (C(2)H(5))(4)N[Ru(NO)Cl(3)(pyca)] was synthesized by the reaction of [Ru(NO)Cl(5)](2)(-) with Hpyca and characterized by X-ray structural analysis: C(14)H(24)N(3)O(3)Cl(3)Ru; triclinic, Ponemacr;, a = 7.631(1), b = 9.669(1), c = 13.627(1) A; alpha = 83.05(2), beta = 82.23(1), gamma = 81.94(1) degrees; V = 981.1(1) A(3); Z = 2. The type II complex of cis-[Ru(NO)Cl(pyca)(2)] was synthesized by the reaction of [Ru(NO)Cl(3)(pyca)](-) or [Ru(NO)Cl(5)](2)(-) with Hpyca and isolated by column chromatography. The structure was determined by X-ray structural analysis: C(12)H(8)N(3)O(5)ClRu; monoclinic, P2(1)/n; a = 10.010(1), b = 13.280(1), c = 11.335(1) A; beta = 113.45(1) degrees; V = 1382.4(2) A(3); Z = 4.     

Silver alkoxide and amino N-heterocyclic carbenes; syntheses and crystal structures

Silver(I) complexes of heterobidentate ligands that incorporate one or two N-heterocyclic carbene moieties coupled with an alcohol or amine group have been made by direct deprotonation of ligands of the form [HOCR¹R²CH₂(1-HC{NCHCHNR})][X], H₂L¹X (X = Br, I), [H₂NR¹CHR²CHR²(1-HC{NCHCHNR})][Br]₂ H₃L²X₂ (X = Cl, Br), and [H₂N{CH₂CH₂(1-HC[NCHCHNMes])}₂][X]₃ H₄L³X₃ (X = Cl, Br). Silver(I) oxide is sufficiently basic to deprotonate both the imidazolium and the alcohol functional groups of all but one of the L¹ ligand precursors, to afford rare examples of silver alkoxide complexes [Ag(L¹)], stabilised by the soft donor carbene. Another complex of L¹ is characterised as the carbene alcohol adduct [Ag(HL¹)₂I]. The analogous reactions of silver(I) oxide with the amino imidazolium precursors afford silver amino-carbenes [Ag(HL²)Br] with the potentially bidentate L² ligand, and [Ag(HL³)X] (X = Cl, Br) with the potentially tridentate L³ ligand. A single crystal X-ray diffraction study of the latter complex confirms that the neutral amine of the potentially tridentate L³ ligand is unco-ordinated; instead the structure contains discrete chains of T-shaped silver bis(carbene) halide moieties that bridge to form a zig-zag 2-connected polymer. Protonolysis of two of the silver alkoxide and amino adducts, [Ag(L^1a)] and [Ag(HL^2a)Br], affords imidazolium complexes salts [H₂L^1a][AgCl₂] and [Ag(H₂L^2a)Br][AgBr₂] that retain the Ag(I) centre as complex counterions. The single crystal X-ray structures of these salts have been determined and show the silver(I) cations are now incorporated into ladders or chains as silver(I) halo-anions, and a silver amine dative bond is present in the latter complex.     

Copper(I) coordination polymers of 2,2'-dipyridylamine derivatives: syntheses, structures, and luminescence

Reactions of CuX (X = Br(-), I(-) or CN(-)) with various types of 2,2'-dipyridylamine (dpa) derivatives have been performed via a hydrothermal-solvothermal method and the products have been structurally characterized by X-ray crystallography. Four ligands with different coordination motifs were employed in the reactions, including angular N,N,N',N'-tetra(2-pyridyl)-2,6-pyridinediamine (tppda); linear N,N,N',N'-tetra(2-pyridyl)-1,4-phenylenediamine (tppa) and N,N,N',N'-tetra(2-pyridyl)biphenyl-4,4'-diamine (tpbpa); and star-shaped tris-[4-(2,2'-dipyridylamino)-phenyl]amine (tdpa), which yielded eight copper(I) complexes exhibiting different stoichiometries of Cu-dpa and variable coordination modes of dpa. The compound [Cu(2)(tppda)(μ-I)(2)](n) (1) forms a one dimensional (1D) coordination polymer exclusively through double μ(2)-I bridges, which arranges to two dimensional (2D) metal-organic frameworks (MOFs) via the face-to-face π···π stacking interactions from pyridyl rings. The compound [Cu(6)(tppa)(μ(3)-Br)(6)](n) (2) forms a 2D network linked through multiple μ(3)-Br bridges. The compound [Cu(2)(tppa)(μ-CN)(2)](n) (3) is also a 2D MOF containing 1D (CuCN)(n) chains. The compounds [Cu(tpbpa)Br](n) (4) and [Cu(4)(tpbpa)(2)(μ-I)(4)](n) (5) display two different 1D assemblies: a zig-zag chain for 4 and a linear structure for 5. The compound [Cu(4)(tpbpa)(μ-CN)(4)](n) (6) shows a pseudo-4,8(2) topological net, while the compound [Cu(8)(tpbpa)(μ-CN)(8)](n)·2nH(2)O (7) exhibits a three-dimensional (3D) framework containing a ···PM··· double helical structure, although both of them contain (CuCN)(n) chains. The compound [Cu(2)(tdpa)(μ-I)(2)](n) (8) is a zig-zag chain based on the star-shaped molecule tpda, in which one of three dpa-arms is free of coordination to metal ions. All complexes exhibit luminescence in the solid state.     

Solvothermal syntheses and crystal structures of two metal coordination polymers with double-chain structures

Two polymeric complexes, [Cu₂(btec)(phen)₂]_n·(H₂O)_n (1) and [Cd₄(btec)₂(phen)₄(H₂O)₄]_n (2) (H₄btec=1,2,4,5-benzenetetracarboxylic acid; PHEN=1,10-phenanthroline), were synthesized by solvothermal reactions at 140 °C. Both complex 1 and 2 possess infinite double-chain structures, in which each Cu(II) center has a tetrahedral configuration and the Cd(II) centers adopt triangular prismatic and square-based pyramidal configurations simultaneously. The inter-chain face to face π–π interactions among the aromatic rings of phen and the hydrogen bond interactions between aqua molecules and carboxyl O atoms result in 3-D networks in the two complexes. The ESR spectra study of complex 1 shows that there is negligibly small long-range super-exchange interactions between the Cu(II) atoms via benzenecarboxylate bridging.     

Three-dimensional metal phosphonodicarboxylates with GIS-zeolite topology: syntheses, structures and magnetic studies

Compounds [M(2)(4-pi)(H(2)O)(4)]·1.5H(2)O [M(II) = Mn(1), Co(2), Ni(3)] and a heterometallic analogue [Co(1.14)Ni(0.86)(4-pi)(H(2)O)(4)]·1.5H(2)O (4) have been synthesized utilizing a rigid 4-phosphonoisophthalic acid (4-piH(4)). Compounds 1-4 are isostructural, confirmed by their powder XRD measurements. Single crystal structural determinations of 1 and 2 reveal that these compounds display a novel pillared layered open framework structure with zeolite gismondine (GIS) topology. Within the layer, edge-sharing {MO(6)} octahedra are found, which are connected by carboxylate and phosphonate groups along the c- and b-axis, respectively. Dominant antiferromagnetic interactions are propagated between the magnetic centers in 1, 2 and 4. While in 3, ferromagnetic exchange couplings are observed.     

Three lanthanide coordination polymers with nitrilotriacetic acid: hydrothermal syntheses,crystal structures and fluorescent property

Hydrothermal reactions of Sm₂O₃, Gd(ClO₄)₃?·?6H₂O and Tb(ClO₄)₃?·?6H₂O with nitrilotriacetic acid, give rise to three lanthanide coordination polymers, {[Sm(NTA)(H₂O)₂]?·?H₂O} _n (1), {[Gd(NTA)(H₂O)]?·?H₂O} _n (2) and {[Tb(NTA)(H₂O)]?·?H₂O} _n (3). Their solid-state structures have been characterized by elemental analysis, and IR spectroscopy. X-ray single-crystal diffraction analyses indicated that 2 and 3 are isomorphous three-dimensional coordination polymers with eight-coordinate Gd(III) (or Tb(III)), while 1 forms a two-dimensional coordination polymer containing nine-coordinate Sm(III). The photophysical properties of 3 have been studied with excitation and emission spectra, which exhibit strong green emission.     

A conformationally flexible, urea-based tripodal anion receptor: solid-state, solution, and theoretical studies

Tripodal tris(urea) cationic receptors 1 and 2 containing p-tolyl or octyl substituents, respectively, have been synthesized, and their association behavior with anionic guests has been studied via a variety of methods. The receptors are based around a hexasubstituted aryl core and contain both urea and pyridinium functionalities. For 1:1 complexes, anions reside within the central cavity of the host species, held by hydrogen bonds from both NH and CH donors. The following host-anion complexes have been characterized by X-ray crystallography: 1-(Br)3, 1-(PF6)3.2(CH3)2CO, and 1-(NO3)1.5(PF6)1.5. Each structure contains the receptor in a significantly different geometry, highlighting the anion-dependent conformational flexibility of 1. Solution 1H NMR spectroscopic titrations have shown the two host species to display significant affinity for both halides and hydrogen sulfate and strongly suggest the persistence of CH...X- interactions despite the presence of "stronger" NH donor groups. Variable-temperature 1H NMR studies on the more soluble octyl derivative 2 show that there is a distinct change in conformation associated with the formation of a 1:1 host/guest complex. Computations using density functional theory (with the B3LYP functional) have been employed to aid in understanding the geometry of the 1:1 host/chloride complexes of 1 and 2. These experiments suggest that the lowest energy conformation for 1-Cl is one in which the ureidopyridinium arms are orientated upward forming a cavity that is sealed by CH...pi interactions, effectively forming a unimolecular capsule, whereas for 2 a less symmetrical "2-up, 1-down" geometry is favored.     

Solventothermal syntheses, structures and photoluminescence of two-dimensional lanthanide coordination polymers with adipic acid

Four lanthanide coordination polymers formulated as [Ln₂(Ad)₃(H₂O)₄] · 0.25H₂O ( Ln = Tb (I), Pr (II), Ho (III), Dy (IV); H₂Ad = adipic acid), have been solventothermally synthesized from the self-assembly of the lanthanide ions (Ln³⁺) with the exible adipic dicarboxylate ligand. All of them were characterized by IR spectroscopy and single-crystal X-ray diffraction. Structural analyses revealed that these complexes had intricate two-dimensional interpenetrated metal-organic networks. In addition, the photoluminescent properties of complex I was discussed in detail, which shows strong green emission, corresponds to ⁵ D ₄ → ⁷ F ₅ transition of Tb³⁺ ions.     

Silver iodobismuthates: syntheses, structures, properties, and theoretical studies of [Bi2Ag2I10 2-]n and [Bi4Ag2I16 2-]n

Two novel silver iodobismuthates have been obtained: (Et4N)2n-[Bi2Ag2I10]n (1) with one-dimensional infinite chains built from bimetallic tetranuclear units and (Et4N)2n[Bi4Ag2I16]n (2) with a two-dimensional 44 grid assembly of the tetranuclear Bi4I16 subunits as nodes and Ag atoms as linkages. Their optical band gaps, 2.05 and 1.93 eV, fit nicely in a size correlation of the Bi/I subunit, which is further supported by the density functional theory studies.     

Hydrothermal syntheses,and crystal structures of new lanthanide coordination polymers with nitrilotriacetic acid

Hydrothermal reactions of Nd(ClO₄)₃·6H₂O, Gd(ClO₄)₃·6H₂O and Er₂O₃ with H₃NTA (nitrilotriacetic acid) afford three new lanthanide coordination polymers, {[Nd(NTA)(H₂O)]· 2H₂O} _n (1), {[Gd(NTA)(H₂O)]·2H₂O} _n (2) and {[Er(NTA)(H₂O)]·H₂O} _n (3), characterized by elemental analysis and IR spectroscopy. X-ray single crystal structural analyses showed that 1 and 2 are an isomorphous 2D-layered framework containing the nine-coordinated Nd(III) (or Gd(III)), and woven into a 3D suprastructure by interlayer hydrogen bonding while 3 is a 3D structure with eight-coordinate Er(III).     

N-donor co-ligand-driven zinc coordination polymers based upon a bithiophene dicarboxylate: syntheses,structures, and luminescent properties

Three zinc compounds assembled from a bithiophene dicarboxylic acid (H₂DMTDC) and different N-donor co-ligands, [Zn(DMTDC)(bpt)(H₂O)]_n (1), {[Zn(DMTDC)(5,5-dmbpy)]·0.5DMF·1.5H₂O}_n (2), and {[Zn(DMTDC)(1,3-bimb)]·2DMF·H₂O}_n (3) (H₂DMTDC?=?3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid, bpt?=?4-amino-3,5-bis(4-pyridyl)1,2,4-triazole, 5,5′-dmbpy?=?5,5′-dimethyl-2,2′-bipyridyl, 1,3-bimb?=?1,3-bis(imidazol-1ylmethyl)benzene), were solvothermally synthesized and characterized. Compounds 1 and 2 are 1-D linear and zigzag chains with different supramolecular structures. In 1, adjacent chains form zipper-like structures through N–H?N interactions. In 2, however, chains in adjacent layers are stacked in an unusual unparallel level through C–H?O interactions. Compound 3 features a highly corrugated 2-D (4,4) layer and the layers are penetrated by each other to give 3-D polycatenations. Right- and left-handed helical Zn-bimb chains are arranged alternately within and between the layers, leading to mesomeric property of the whole network. Thermal stability and the decomposed products of all compounds were investigated. Luminescent properties of the ligands and compounds in the solid state at room temperature have also been explored. Moreover, the luminescence intensities of the compounds in different solvents are largely dependent on the solvent.     

2D coordination polymers of macrocyclic oxamide with polycarboxylates: syntheses, crystal structures and magnetic properties

Five new 2D coordination polymers, [Co(nip)(CuL)(H(2)O)]·CH(3)OH (1), [Mn(ip)(NiL)]·0.63H(2)O (2), [Cu(ip)(CuL)] (3), [Mn(6)(CuL)(6)(btc)(4)(H(2)O)(4)]·7H(2)O (4), and [Cu(CuL)(Hbtc)(H(2)O)] (5)(ML, H(2)L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-diene; H(2)nip = 5-nitroisophthalic acid; H(2)ip = m-isophthalic acid; H(3)btc = 1,3,5-benzenetricarboxylic acid) have been synthesized by a solvothermal method and characterized by single-crystal X-ray diffraction. Complexes 1-5 exhibit different 2D layered structures formed by Co(2)Cu(2) (1), Mn(2)Ni(2) (2), Cu(4) (3), Mn(3)Ni(3) (4), Cu(4) (5) units, respectively, via the oxamide and diverse carboxylic acid bridges. Compounds 1, 2, 3 and 5 are uninodal 4-connected (4, 4)-grids topology, while complex 4 possesses a 2D network with (3, 4)-connected (4(2).8)(4)(4(3).6(2).8)(3) topology. The results of magnetic determination show pronounced antiferromagnetic interactions in 1-4.     

Diverse lanthanide coordination polymers tuned by the flexibility of ligands and the lanthanide contraction effect: syntheses, structures and luminescence

Two new flexible exo-bidentate ligands were designed and synthesized, incorporating different backbone chain lengths bearing two salicylamide arms, namely 2,2'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))bis(N-benzylbenzamide) (L(I)) and 2,2'-(2,2'-(ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(oxy)bis(N-benzylbenzamide) (L(II)). These two structurally related ligands are used as building blocks for constructing diverse lanthanide polymers with luminescent properties. Among two series of lanthanide nitrate complexes which have been characterized by elemental analysis, TGA analysis, X-ray powder diffraction, and IR spectroscopy, ten new coordination polymers have been determined using X-ray diffraction analysis. All the coordination polymers exhibit the same metal-to-ligand molar ratio of 2?:?3. L(I), as a bridging ligand, reacts with lanthanide nitrates forming two different types of 2D coordination complexes: herringbone framework {[Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)](∞) (Ln = La (1), and Pr (2), m = 1, 2)} as type I,; and honeycomb framework {[Ln(2)(NO(3))(6)(L(I))(3)·nCH(3)OH](∞) (Ln = Nd (3), Eu (4), Tb (5), and Er (6), n = 0 or 3)} as type II, which change according to the decrease in radius of the lanthanide. For L(II), two distinct structure types of 1D ladder-like coordination complexes were formed with decreasing lanthanide radii: [Ln(2)(NO(3))(6)(L(II))(3)·2C(4)H(8)O(2)](∞) (Ln = La (7), Pr (8), Nd (9)) as type III, [Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)·nCH(3)OH](∞) (Ln = Eu (10), Tb (11), and Er (12), m, n = 2 or 0) as type IV. The progressive structural variation from the 2D supramolecular framework to 1D ladder-like frameworks is attributed to the varying chain length of the backbone group in the flexible ligands. The photophysical properties of trivalent Sm, Eu, Tb, and Dy complexes at room temperature were also investigated in detail.