Hydrothermal syntheses,structures, and properties of four metal–organic coordination polymers assembled from V-shaped tetracarboxylate ligands and N-donor ancillary ligands

A series of four metal–organic frameworks, namely, [Cu(sdpa)_0.5(2,2′-bpy)]·H₂O (1), [Zn₂(sdpa)(2,2′-bpy)₂(H₂O)₂]·3H₂O (2), [Zn₂(sdpa)(4,4′-bpy)]·3H₂O (3), [Cd₂(sdpa)(4,4′-bpy)_1.5(H₂O)₂](4), have been hydro(solvo)thermally synthesized through the reaction of 2,3,2′,3′-sulfonyldiphthalic acid (H₄sdpa) with divalent copper, zinc and cadmium salts in the presence of ancillary nitrogen ligands (4,4′-bpy = 4,4′-bipyridine, 2,2′-bpy = 2,2′-bipyridine) and structurally characterized by elemental analysis, IR and X-ray diffraction. Both complex 1 and 2 show metal–organic chain structure, and the adjacent chains are further linked by π?π and C–H?π interactions for 1 and hydrogen bonds and π?π interactions for 2 to form 3D supramolecular structure. In complex 3, two Zn1 and two Zn2 atoms appear alternately and are bridged by sdpa⁴⁻ anion ligands to form an infinite Zn-sdpa chain. Such chains are further linked together through 4,4′-bpy ligands in four orientations to form a robust 3D metal–organic network. In compound 4, a 3D Cd-sdpa metal–organic network is accomplished through sdpa⁴⁻ anion ligands, and further stabilized by 4,4′-bpy in six orientations. Their luminescence and thermal analysis have also been investigated.     

Synthesis,structure, and magnetic properties of lanthanide ferrocenoylacetonates with nitrate and 2,2′-bipyridine ligands

Ferrocenoylacetonate complexes of several lanthanides, [Ln(fca)₂(NO₃)(bpy)]·nMeC₆H₅ (Ln = Sm (1), Dy (3), Er (4), Yb (5), n = 1; Eu (2), n = 0.5; fca = FcC(O)CHC(O)Me; bpy = 2,2′-bipyridine), were synthesized and characterized by X-ray single-crystal analysis. Complexes 1, 4, and 5 are isostructural; 2 has a similar molecular structure with cis-disposition of fca ligands. The molecular structure of 3 is different, with trans-disposition of the fca ligands. Crystal lattices of the complexes are stabilized by π-stacking interactions. The Ln³⁺ ions in the complexes are eight-coordinate. According to mass spectroscopic data, the complexes are unstable in the gas phase. Magnetic properties of 2 and 4 were studied in a DC field; for 4, AC studies were also carried out. The values of spin-orbital parameters obtained using two estimation methods for 2 are in satisfactory agreement. Slow relaxation of the magnetization was found for the Er complex.     

Synthesis,structure, and magnetic properties of iron — yttrium complexes containing acetylacetonate ligands

Two new compounds have been obtained by the synthesis of heteronuclear iron-yttrium acetylacetonate, using the modified electrochemical dissolution of the [YFe₂] alloy. One of these compounds, with the Fe(acac)₂ · 2H₂O composition, has been studied by X-ray diffraction analysis. X-ray diffraction data: a=11.002(5), b=5.412(2), c=11.179(5) Å;=106.39(4)°;V=638.6 ų, space group P2₁/c, Z=2. According to the data on magnetic susceptibility, Mössbauer spectroscopy, and X-ray electron microanalysis, single crystals of this complex are covered with an amorphous film containing finely dispersed [Y_1–aFe_a]n clusters and, probably, superparamagnetic -Fe₂O₃ species. The second oligomeric acetylacetonate complex contains ions of high-spin two-valence iron, yttrium, and finely dispersed ferromagnetic [Y_1–aFe_a)n intermetallide clusters.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1454–1458, August, 1995.The studies were financially supported by the International Science Foundation (Grants Nos. MI 8000, MI 8300).     

Synthesis,characterization, and photoluminescence properties of difluoroboron complexes with bis-β-diketone ligands

Some novel difluoroboron bis-β-diketonates containing a pyridyl moiety were synthesized from diethyl 2,6-pyridinedicarboxylate via Claisen condensation with the corresponding aryl methyl ketones and followed by complexation with boron trifluoride etherate. Their spectroscopic behaviors were studied by FTIR, ¹H NMR, UV–Vis, and fluorescence spectroscopic techniques. The results indicated that difluoroboron bis-β-diketonates exhibited violet or blue fluorescence emission at 428–454 nm under UV illumination in DMSO and possessed high extinction coefficients. It was found that the nature of the substituents at benzene ring in bis-β-diketone ligands had a significant impact on the photoluminescence behaviors of difluoroboron complexes. The complex 5b exhibited the strongest photoluminescence intensity and highest quantum yield (Φ _u = 0.93), due to two strong electron-donating methoxyl moieties in molecule and the compound 4b displayed the lowest photoluminescence intensity and quantum yield, assigned to the heavy atom effect of the chlorine atom in its molecule. The photoluminescence intensity and quantum yield of these difluoroboron complexes decreased in the sequence, 5b > 2b > 1b > 3b > 4b.     

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 structures, photophysical properties, and bioimaging of living cells of bis-β-diketonate phenothiazine ligands and its cyclic dinuclear complexes

Two bis-β-diketones, RCOCH(2)CO-EPTZ-COCH(2)COR (EPTZ = 10-ethylphenothiazine; R = C(6)H(5) for H(2)L(1) and CF(3) for H(2)L(2)) and their cyclic dinuclear Zn(II), Cd(II), Ni(II), Mn(II), Cu(II), Co(II) complexes have been synthesized and fully characterized. Their crystal structures were determined by single crystal X-ray diffraction analysis. Their photophysical properties have been further investigated both experimentally and theoretically. The results revealed that significant enhancement of two-photon absorption cross section values were obtained for the cyclic dinuclear Zn(II) and Cd(II) complexes compared with their free ligands. Additionally, confocal microscopy and two-photon microscopy fluorescent imaging of MCF-7 cells labeled with two ligands and Zn(II) complexes reveal their potential applications as a biological fluorescent probe.     

Ruthenium complexes of 4,4′-bi-1,2,3-thiadiazole and azoimine ligands: syntheses,crystallography, and electrochemical studies

Abstract  

Five ruthenium complexes of the general type trans-[Ru^II(btd)(Azo)Cl₂] ({Azo = PhN=NC(COMe) = NC₆HY, where Y = H (a), Me (b), OMe (c), Cl (d) or Br (e)} and btd = 4,4′-bi-1,2,3-thiadiazole) have been prepared by the reaction of RuCl₃ with the ligands in the presence of LiCl. These complexes have been characterized by spectroscopic (IR, UV–Vis, and NMR) and electrochemical techniques. In addition, the complex trans-[Ru^II(btd)(L5)Cl₂] (complex 5) has been characterized by X-ray diffraction analysis. The electrochemical parameter for the π-excessive ligand (btd) is reported. The absorption spectrum of complex 5 in acetonitrile has been modeled by time-dependent density functional theory.     

pH-dependent syntheses and crystal structures, characterizations, and DFT calculations of complexes with 2,2′-biimidazole and terephthalic acid ligands

The divalent transition metal complexes [Zn(L)₂(H₂O)₂](Tere) (I), [Cd(L)₂(H₂O)₂](Tere]) (II) and [Cd(L)₂(HTere)₂] (III) (L = 2,2’-biimidazole, Tere = terephthalate) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectrum, thermal analysis and single-crystal X-ray diffraction analysis. Complexes II and III have the same starting materials but possess different frame-works and are prepared from H₂Biim and H₂Tere under hydrothermal conditions with different pH values. The crystal structures show I and II have the same coordination circumstances and are coordinated by two H₂O molecules and two neutral bidentate 2,2′-biimidazole ligands. The terephthalate acts as the counter anion. In contrast, complex III contains protonated carboxylate groups coordinated to the metal centre to give neutral species. Furthermore, based on the optimized structures, molecular frontier orbitals, Mulliken charges and IR spetra of complex I and III are investigated by density functional theory. Calculated results show that the energy gap (ΔE _L-H) between HOMO and LUMO of complex III is bigger than that of I. It is revealed that complex III is more stable, and this calculated estimation corresponds with experimental analysis of TGA curves.     

Synthesis,structure, and spectroscopy of two benzil-based α-diimine ligands and their palladium(II) complexes

Two α-diimine ligands were prepared in 60–70% yield via p-toluenesulfonic acid-catalyzed condensation reactions from benzil with 4-bromoaniline and with p-anisidine. Palladium(II) complexes were prepared from both ligands in 70–80% yield. X-ray structures were obtained for the ligand prepared from p-anisidine and its palladium(II) complex. A notable feature observed in the former was its unconjugated C–N double bonds, both in the (E)-configuration. The latter structure possessed two molecules of the metal complex in its unit cell, both of which have diimine cores with a degree of conjugation and a nonideal square-planar geometry around palladium caused by the small bite angles (79.61(3) and 79.15(3)°) of the diimine ligands. Solution-phase electronic absorption spectra of the ligands in chloroform have two bands from π→π ^? and n→π ^? transitions at 269–345?nm. Absorption spectra of the complexes in chloroform exhibited bands attributed to ligand-centered transitions that were red-shifted as compared to free ligands. Only the spectrum obtained from a chloroform solution of the palladium(II) complex with the diimine ligand prepared from p-anisidine featured a band at approximately 520?nm, which was assigned to a combination of d _π(Pd)→π ^? and n(Cl)→π ^? transitions.     

Synthesis, characterization, and multielectron reduction chemistry of uranium supported by redox-active α-diimine ligands

Uranium compounds supported by redox-active α-diimine ligands, which have methyl groups on the ligand backbone and bulky mesityl substituents on the nitrogen atoms {(Mes)DAB(Me) = [ArN═C(Me)C(Me)═NAr], where Ar = 2,4,6-trimethylphenyl (Mes)}, are reported. The addition of 2 equiv of (Mes)DAB(Me), 3 equiv of KC(8), and 1 equiv of UI(3)(THF)(4) produced the bis(ligand) species ((Mes)DAB(Me))(2)U(THF) (1). The metallocene derivative, Cp(2)U((Mes)DAB(Me)) (2), was generated by the addition of an equimolar ratio of (Mes)DAB(Me) and KC(8) to Cp(3)U. The bond lengths in the molecular structure of both species confirm that the α-diimine ligands have been doubly reduced to form ene-diamide ligands. Characterization by electronic absorption spectroscopy shows weak, sharp transitions in the near-IR region of the spectrum and, in combination with the crystallographic data, is consistent with the formulation that tetravalent uranium ions are present and supported by ene-diamide ligands. This interpretation was verified by U L(III)-edge X-ray absorption near-edge structure (XANES) spectroscopy and by variable-temperature magnetic measurements. The magnetic data are consistent with singlet ground states at low temperature and variable-temperature dependencies that would be expected for uranium(IV) species. However, both complexes exhibit low magnetic moments at room temperature, with values of 1.91 and 1.79 μ(B) for 1 and 2, respectively. Iodomethane was used to test the reactivity of 1 and 2 for multielectron transfer. While 2 showed no reactivity with CH(3)I, the addition of 2 equiv of iodomethane to 1 resulted in the formation of a uranium(IV) monoiodide species, ((Mes)DAB(Me))((Mes)DAB(Me2))UI {3; (Mes)DAB(Me2) = [ArN═C(Me)C(Me(2))NAr]}, which was characterized by single-crystal X-ray diffraction and U M(4)- and M(5)-edge XANES. Confirmation of the structure was also attained by deuterium labeling studies, which showed that a methyl group was added to the ene-diamide ligand carbon backbone.     

Isosteric expansion of the structural diversity of chiral ligands: Design and application of proline-based N,N′-dioxide ligands for copper-catalyzed enantioselective Henry reactions

Chiral N,N′-dioxide catalysts were designed based on isosteric approach. Using l-Proline as the starting material, a variety of chiral N,N′-dioxide ligands were obtained via conventional functional group transformations and were utilized in asymmetric Henry reactions between nitromethane and aromatic aldehydes. Using the N,N′-dioxide-copper(II) complexes as the catalysts, asymmetric Henry reaction produced the corresponding β-nitroalcohols in up to 66% yields and up to 83% ee's under mild conditions. The reactions were easy to carry out, and special care such as air or moisture-free conditions was not required.     

Synthesis,characterization, and cytotoxicity of Pt(IV) complexes containing 1,10-phenanthroline and 2,2′-bipyridine and diaminocyclohexane ligands

Four platinum(IV) complexes containing intercalating ligands [1,10-phenanthroline (phen) and 2,2′-bipyridine (bpy)] and ancillary ligands [(1S,2S)-diaminocyclohexane (SS-DACH) and (1R,2R)-diaminocyclohexane (RR-DACH)] were synthesized and characterized by ¹H nuclear magnetic resonance, electrospray ionization mass spectrometry, X-ray crystal structure analysis, elemental analysis, ultraviolet absorption spectroscopy, circular dichroism spectroscopy, and electrochemical analysis. The reactions between [Pt(phen)(SS-DACH)Cl₂]²⁺ and glutathione and Ac-CPFC-NH₂ were investigated by high-performance liquid chromatography. [Pt(phen)(SS-DACH)Cl₂]²⁺ was reduced to its corresponding Pt(II) complex [Pt(phen)(SS-DACH)]²⁺, while glutathione and Ac-CPFC-NH₂ were oxidized to glutathione-disulfide and a peptide containing an intramolecular disulfide bond, respectively. The cytotoxicities of the Pt(IV) complexes against a human non-small cell lung cancer cell line (A549) and the corresponding cisplatin-resistant cell line (A549cisR) were evaluated. These Pt(IV) complexes showed a higher activity toward A549 and A549cisR than did cisplatin. Also, the cytotoxicities of the Pt(IV) complexes were higher for A549cisR than for A549 cells. Moreover, the cytotoxicities of the (SS-DACH)-liganded platinum complexes were higher than those of the (RR-DACH)-liganded platinum complexes in either A549 or A549cisR cells. Phen-liganded platinum complexes were more cytotoxic than the bpy-liganded platinum complexes. The cytotoxicities of these Pt(IV) complexes had no correlation with reduction potentials.     

Half-sandwich η-benzene Ru(II) complexes of pyridylpyrazole and pyridylimidazole ligands: Synthesis, spectra, and structure

New series of half-sandwich ruthenium(II) complexes supported by a group of bidentate pyridylpyrazole and pyridylimidazole ligands [(η⁶-C₆H₆)Ru(L²)Cl][PF₆] (1), [(η⁶-C₆H₆)Ru(HL³)Cl][PF₆] (2), [(η⁶-C₆H₆)Ru(L⁴)Cl][PF₆] (3), and [(η⁶-C₆H₆)Ru(HL⁵)Cl][PF₆] (4) [L², 2-[3-(4-chlorophenyl)pyrazol-1-ylmethyl]pyridine; HL³, 3-(2-pyridyl)pyrazole; L⁴, 1-benzyl-[3-(2′-pyridyl)]pyrazole; HL⁵, 2-(1-imidazol-2-yl)pyridine] are reported. The molecular structures of 1-4 both in the solid state by X-ray crystallography and in solution using ¹H NMR spectroscopy have been elucidated. Further, the crystal packing in the complexes is stabilized by C-H?X (X = Cl and π), N-H?Cl, and π-π interactions.     

Synthesis,characterization, and optoelectronic properties of heteroleptic iridium complexes containing substituted 1,3,4-oxadiazole and β-diketone as ligands

The new heteroleptic iridium(III) complexes (BuOXD)₂Ir(tta) and (BuOXD)₂Ir(tmd) [BuOXD?=?2-(4-butyloxyphenyl)-5-phenyl[1,3,4]oxadiazolato-N4,C2, tta?=?1,1,1-trifluoro-4-thienylbutane-2,4-dionato, tmd?=?2,2,6,6-tetramethylheptane-3,5-dionato] have been synthesized and characterized. These complexes have two cyclometalated ligands (C^N) and a bidentate diketone ligand (X) [C^N)₂Ir(X)], where X is a β-diketone with trifluoromethyl, theonyl or t-butyl groups. The color tuning with the change in electronegativity of substituents in the β-diketones has been studied. Photoluminescence spectra of the complexes showed peak emissions at 523 and 549?nm, respectively. The electroluminescent properties of these complexes have been studied by fabricating multi layer devices with device structure ITO/α-NPD/8% iridium complex doped CBP/BCP/Alq₃/LiF/Al. The electroluminescence spectra also showed peak emissions at 526 and 570?nm for (BuOXD)₂Ir(tta) and (BuOXD)₂Ir(tmd), respectively. These metal complexes showed good thermal stability in air to 340°C.     

Analysis of tertiary phosphanes, arsanes, and stibanes as bridging ligands in dinuclear Group 9 complexes

The unusual bridging and semi‐bridging binding mode of tertiary phosphanes, arsanes, and stibanes in dinuclear low‐valent Group 9 complexes have been studied by density functional methods and bonding analyses. The influence of various parameters (bridging and terminal ligands, metal atoms) on the structural preferences and bonding of dinuclear complexes of the general composition [A¹ M¹(μ‐CH₂)₂(μ‐EX₃)M² A²] (M¹, M²=Co, Rh, Ir; A¹, A²=F, Cl, Br, I, κ²‐acac; E=P, As, Sb, X=H, F, CH₃) has been analyzed. A number of factors have been identified that favor bridging or semi‐bridging modes for the phosphane ligands and their homologues. A more symmetrical position of the bridging ligand EX₃ is promoted by more polar E? X bonding, but by less electronegative (softer) terminal anionic ligands. Among the Group 9 metal elements Co, Rh, and Ir, the computations clearly show that the 4d element rhodium exhibits the largest preference for a {M¹(μ‐EX₃)M²} bridge, in agreement with experimental observation. Iridium complexes should be valid targets, whereas cobalt does not seem to support well a symmetric bridging mode. Analyses of the Electron Localization Function (ELF) indicate a competition between a delocalized three‐center bridge bond and direct metal–metal bonding.     

Synthesis, characterization, dynamics and reactivity toward amination of η3-allyl palladium complexes bearing mixed ancillary ligands. Evaluation of the electronic characteristics of the ligands from kinetic data

On the basis of an original protocol, we have synthesized several complexes of the type [Pd(η(3)-C(3)H(3)R(2))(LL')]ClO(4) (R = H, Me; L, L' = PPh(3), P(OEt)(3), 2,6-dimethylphenylisocyanide, t-butylisocyanide, 1,3-dimesitylimidazolidine, 1,3-dimesitylimidazol-2-ylidene). The complexes, some of which are completely new species, were fully characterized and their behaviour in solution was studied by means of (1)H NMR. The reactions of the complexes bearing the symmetric allyl moiety [Pd(η(3)-C(3)H(5))(LL')]ClO(4) with piperidine in the presence of the olefin dimethylfumarate were followed under kinetically controlled conditions. Formation of allyl-amine and of the palladium(0) derivatives [Pd(η(2)-dmfu)(LL'] was observed. The reaction rates k(2) proved to be strongly dependent on the ancillary ligand nature and allowed a direct comparison among the electronic characteristics of the ligands. The reactivity trend determined appears to be mainly influenced by the capability of the ancillary ligands in transferring electron density to the metal centre and consequently on the allyl fragment.     

Study on molecular and electronic structures, and spectroscopic properties of azide ruthenium complexes with pyridine and β-picoline ligands

The [Ru(N₃)₂(PPh₃)(py)₃] and [Ru(N₃)₂(PPh₃)₂(β-pic)₂] complexes have been prepared and studied by IR, NMR, UV-Vis spectroscopy and X-ray crystallography. The complexes were prepared in the reactions of [RuCl₂(PPh₃)₃] with pyridine, β-picoline and NaN₃ in methanol solutions. The electronic structures of the obtained complexes have been calculated using the DFT/TD-DFT method. The trans effect of triphenylphosphine on the pyridine molecule has been studied using NBO and molecular orbital terms, and impact of the acceptor properties of the halide/pseudohalide co-ligands was indicated.     

Zirconium and hafnium amide, alkoxide, and pyrrolyl complexes manifesting with pyrrolyl-linked N-donor ligands: Syntheses, characterization, and ring opening polymerization of ε-caprolactone

A series of zirconium and hafnium alkoxide and amide complexes containing symmetrical tridentate pyrrolyl ligand, [C₄H₂NH(2,5-CH₂NMe₂)₂] have been synthesized conveniently by treatment of 2,6-di-tert-butylphenol, tert-butanol or pyrrole in pentane and their reactivity over ring opening polymerization of ε-caprolactone have been carried out. Reactions of [C₄H₂NH(2,5-CH₂NMe₂)₂] with M(NEt₂)₄ (M = Zr or Hf) originate [C₄H₂N(2,5-CH₂NMe₂)₂]M(NEt₂)₃ (1, M = Zr; 2, M = Hf). Furthermore, reactions of [C₄H₂N(2,5-CH₂NMe₂)₂]M(NEt₂)₃ with 2,6-di-tert-butylphenol, tert-butanol or pyrrole afford [C₄H₂N(2,5-CH₂NMe₂)₂]M(OC₆H₃-2,6-^tBu₂)(NEt₂)₂ (3, M = Zr; 4, M = Hf), [C₄H₂N(2,5-CH₂NMe₂)₂]M(O^tBu)₃ (5, M = Zr; 6, M = Hf) and [C₄H₂N(2,5-CH₂NMe₂)₂]M(C₄H₄N)₃ (7, M = Zr; 8, M = Hf), respectively, in satisfactory yield. All the complexes have been characterized by NMR spectra as well 3, 4 and 6 subjected to the X-ray diffraction analysis. Complexes 3-8 have been used as initiators for the ring-opening polymerization of ε-caprolactone and observed broad PDI values (1.84-2.75) representing multiple reactivity centers of these complexes.     

Syntheses,crystal structures,and characterization of three metal–organic complexes with 2,2′-biphenyldicarboxylic acid and phenanthroline ligands

Three complexes constructed with 2,2′-biphenyldicarboxylic acid, multidentate nitrogen donors, and metal salts, {[Cd(2,2′-dpdc)(tppp)(H₂O)]₂?·?2H₂O} _n (1), {[Pb(2,2′-dpdc)(pyphen)]₂} _n (2), and {[Pb(2,2′-dpdc)(dppz)]} _n (3) (H₂dpdc = 2,2′-diphenyldicarboxylic acid; tppp = 4-(1H-1,3,7,8-tetraazacyclopenta[l]phenanthren-2-yl)phenol; pyphen?=?pyrazino[2,3-f]-[1,10]phenanthroline; and dppz = dipyrido[3,2-a:2′,3′-c]phenazine), are synthesized under hydrothermal conditions. These complexes are characterized by single-crystal X-ray diffraction, elemental analysis, IR, TGA, and photoluminescence. In 1, two 2,2′-dpdc ions bridge two Cd(II) ions to form an isolated cluster with Cd?···?Cd distance of 5.023(4)?Å. These clusters are further linked by intermolecular hydrogen bonds, yielding a 2-D supramolecular structure. Complex 2 contains two crystallographically independent Pb(II) ions in the asymmetric unit. Pb1 ions are bridged by 2,2′-dpdc anions to form a chain along the x-axis. Two Pb2 ions are coordinated by two 2,2′-dpdc anions and two pyphen ligands to form a cluster. These clusters are linked by π–π interactions to yield a 1-D supramolecular chain along the y-axis. In 3, neighboring Pb(II) atoms are bridged by 2,2′-dpdc anions to form a 1-D chain structure. Further, the chains are linked into a 3-D supramolecular network through aromatic π–π interactions.