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Vadapalli Chandrasekhar

Publications and source records attributed to Vadapalli Chandrasekhar.

At least 19 recordsLinked to original sources
PubMed2006

Inorganic-cored photoactive assemblies: synthesis, structure, and photochemical investigations on stannoxane-supported multifluorene compounds.

Organostannoxanes were used as inert supports for the preparation of multichromophore assemblies. The synthesis involves a single-step procedure and allows the preparation of compounds in which the number of chromophore units can be varied from one to six. Thus, the reactions of LCOOH (1-fluorenecarboxylic acid) or L'COOH (9-fluorenecarboxylic acid) with various organostannoxane precursors afforded the fluorenyl derivatives [Ph(3)SnO(2)CL] (1), [Ph(3)SnO(2)CL'] (2), [{nBu(3)SnO(2)CL''}(n)] (3), [{nBu(3)SnO(2)CL'}(n)] (4), [{tBu(2)Sn(OH)O(2)CL}(2)] (5), [{tBu(2)Sn(OH)O(2)CL'}(2)] (6), [{[nBu(2)SnO(2)CL](2)O}(2)] (7) [{[nBu(2)SnO(2)CL'](2)O}(2)] (8), [{nBuSn(O)O(2)CL}(6)] (9), and [{nBuSn(O)O(2)CL'}(6)] (10). Interestingly, the formation of 3 is accompanied by an unusual oxo-transfer reaction. The ligand L is oxidized at the 9-position. Compounds 1, 3, 5, 7, and 8 were characterized by X-ray crystallography. The solid-state structures of these compounds reveal rich supramolecular structures owing to multiple intermolecular interactions between the various supramolecular synthons present in these molecules. The optical behavior of 1-10 is primarily dictated by the fluorenyl periphery. These compounds display strong blue fluorescent emission in solution and blue-green fluorescent emission in the solid state. Fluorescence lifetimes of all of these compounds are on the nanosecond timescale, and this suggests that the emission originates from the singlet excited state to the ground state. Intermolecular interactions in the solid state lead to considerable broadening of the emission bands.

Journal Article↗
PubMed2006

Di- and trinuclear complexes derived from hexakis(2-pyridyloxy)cyclotriphosphazene. Unusual P-O bond cleavage in the formation of [{(L'CuCl)2(Co(NO3)}Cl] (L' = N3P3(OC5H4N)5(O)).

Hexakis(2-pyridyloxy)cyclotriphosphazene (L) is an efficient multisite coordination ligand which binds with transition metal ions to produce dinuclear (homo- and heterometallic) complexes [L(CuCl)(CoCl3)], [L(CuCl)(ZnCl3)], [L(CoCl)(ZnCl3)], and [L(ZnCl2)2]. In these dinuclear derivatives the cyclophosphazene ligand utilizes from five to six nitrogen coordination sites out of the maximum of nine available sites. Further, the spacer oxygen that separates the pyridyl moiety from the cyclophosphazene ring ensures minimum steric strain to the cyclophosphazene ring upon coordination. This is reflected in the near planarity of the cyclophosphazene ring in all the dinuclear derivatives. In the dinuclear heterobimetallic derivatives one of the metal ions [Cu(II) or Co(II)] is hexacoordinate and is bound by the cyclophosphazene in a eta5-gem-N5 mode. The other metal ion in these heterobimetallic derivatives [Co(II) or Zn(II)] is tetracoordinate and is bound in an eta(1)-N(1) fashion. In the homobimetallic derivative, [L(ZnCl2)2], one of the zinc ions is five-coordinate (eta3-nongem-N3), while the other zinc ion is tetracoordinate(eta2-gem-N2). The reaction of L with CuCl2 followed by Co(NO3)2.6H2O yields a trinuclear heterobimetallic complex [{(L'CuCl)2Co(NO3)}Cl] [L' = N3P3(OC5H4N)5(O)]. In the formation of this compound an unusual P-O bond cleavage involving one of the phosphorus-pyridyloxy bonds is observed. The molecular structure of [{(L'CuCl)2Co(NO3)}Cl] [L' = N3P3(OC5H4N)5(O)] reveals that each of the two the P-O-cleaved L' ligands is involved in binding to Cu(II) to generate the motif L'CuCl. Two such units are bridged by a Co(II) ion. The coordination environment around the bridging Co(II) ion contains four oxygen (two P-O units, one chelating nitrate) and two nitrogen atoms (pyridyloxy nitrogens).

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PubMed2006

Assembly of lipophilic tetranuclear (Cu4 and Zn4) molecular metallophosphonates from 2,4,6-triisopropylphenylphosponic acid and pyrazole ligands.

A sterically hindered aryl phosphonic acid ArP(O)(OH)2 (2) (Ar = 2,4,6-isopropylphenyl) was synthesized and structurally characterized. ArP(O)(OH)2 forms an interesting hydrogen-bonded corrugated sheet-type supramolecular structure in the solid-state. A three-component reaction involving ArP(O)(OH)2, 3,5-dimethylpyrazole(DMPZH), and Cu(CH3COO)2.H2O produces the tetranuclear Cu(II) compound [Cu4(mu3-OH)2{ArPO2(OH)}2(CH3CO2)2(DMPZH)4][CH3COO]2.CH2Cl2 (3). A similar three-component reaction involving ArP(O)(OH)2, 3,5-dimethylpyrazole, and Zn(CH3COO)2.2H2O yields the tetranuclear Zn(II) compound [Zn4{ArPO3}2{ArPO2(OH)}2{DMPZH}4(DMPZ)2].5MeOH (4). While 3 has been found to have an asymmetric cage structure where two dinuclear copper cores are bridged by bidentate [ArPO2(OH)]- ligands, 4 possesses an open-book tricyclic structure composed of three fused metallophosphonate rings. Magnetic studies on 3 revealed antiferromagnetic behavior.

Journal Article↗
PubMed2005

Organostannoxane-supported multiferrocenyl assemblies: synthesis, novel supramolecular structures, and electrochemistry.

Organostannoxane-based multiredox assemblies containing ferrocenyl peripheries have been readily synthesized by a simple one-pot synthesis, either by a solution method or by room-temperature solid-state synthesis, in nearly quantitative yields. The number of ferrocenyl units in the multiredox assembly is readily varied by stoichiometric control as well as by the choice of the organotin precursors. Thus, the reaction of the diorganotin oxides, R2SnO (R = Ph, nBu and tBu) with ferrocene carboxylic acid affords tetra-, di-, and mononuclear derivatives [{Ph2Sn[OC(O)Fc]2}2] (1), [{[nBu2SnOC(O)Fc]2O}2] (2), [nBu2Sn{OC(O)Fc}2] (3), [{tBu2Sn(OH)OC(O)Fc}2] (4), and [tBu2Sn{OC(O)Fc}2] (5) (Fc = eta(5)C5H4-Fe-eta(5)C5H5). The reaction of triorganotin oxides, R3SnOSnR3 (R = nBu and Ph) with ferrocene carboxylic acid leads to the formation of the mono-nuclear derivatives [Ph3SnOC(O)Fc] (6) and [{nBu3SnOC(O)Fc}(n)] (7). Molecular structures of the compounds 1-4 and 6 have been determined by single-crystal X-ray analysis. The molecular structure of compound 1 is new among organotin carboxylates. In this compound, ferrocenyl carboxylates are involved in both chelating and bridging coordination modes to the tin atoms to form an eight-membered cyclic structure. In all of these compounds, the acidic protons of the cyclopentadienyl groups are hydrogen bonded to the carboxylate oxygens (C-HO) to form rich supramolecular assemblies. In addition to this, pi-pi, T-shaped, L-shaped, and side-to-face stacking interactions involving ferrocenyl groups also occur. Compound 6 shows an interesting and novel intermolecular CO2-pi stacking interaction. Electrochemical analysis of the compounds 1-4, 6, and 7 shows a single, quasi-reversible oxidation peak corresponding to the simultaneous oxidation of four, two, and one ferrocenyl substituents, respectively. Compound 5 shows two quasi-reversible oxidation peaks. This is attributed to the positional difference among the ferrocenyl substituents on the tin atom. Additionally, while compounds 2 and 4 are electrochemically quite robust and do not decompose even after ten continuous CV cycles, compounds 1, and 3, 5-7 start to show decomposition after five cycles.

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PubMed2005

A new structural form for a decanuclear copper(II) assembly.

The synthesis and structure of a novel decanuclear copper(II) cage is reported. The assembly of the cage is facilitated by the cumulative coordinative interaction of tert-butyl phosphonate, 2-pyridylpyrazole and hydroxide ligands with copper(II) ions. Magnetic studies of this decanuclear copper(II) cage indicate complex antiferromagnetic behaviour.

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PubMed2005

Synthesis, structure, and stereochemistry of trinuclear metal complexes formed from the phosphorus-based achiral tripodal ligand {P(S)[N(Me)N=CHC6H4-o-OH]3} (LH3): luminescent properties of L2Cd3 x 2H2O.

Neutral trinuclear metal complexes L2Cd3 x 2H2O, L2Mn3 x MeOH, and L2Zn3 x MeOH were isolated in the reaction between the phosphorus-centered achiral tris(hydrazone) P(S)[N(Me)N=CHC6H(4)-o-OH]3 (LH3) and the corresponding divalent metal ions. The trinuclear complexes contain two equivalent terminal metal ions (M(t)) and a central metal ion (M(c)). The ligand encapsulates M(t) in a facial N3O3 coordination environment. From the coordination sphere of the two terminal metal ions a pair of phenolic oxygen atoms further coordinate to the central metal ion. The coordination requirements of M(c) are completed by the solvents of coordination. The achiral trianionic tripodal ligand (L)3- induces chirality in the metal complexes. This results in a delta (clockwise) or lambda (anticlockwise) configuration for the terminal metal ions. The enantiomeric complexes 2-4 (delta-delta or lambda-lambda) crystallize as racemic compounds. The supramolecular structures of 2-4 reveal chiral recognition in the solid-state; every molecule with the delta-delta configuration interacts stereospecifically, through C-H...S=P bonds, with two lambda-lambda molecules to generate a one-dimensional polymeric chain. Photophysical studies of the diamagnetic trinuclear complexes reveal that the tricadmium complex is luminescent in the solid state as well as in solution. In contrast LH3 and L2Zn3 x MeOH are nonluminescent.

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PubMed2004

Control of molecular topology and metal nuclearity in multimetallic assemblies: designer metallosiloxanes derived from silanetriols.

Lipophilic N-bonded silanetriol RSi(OH)(3) (R=(2,6-iPr(2)C(6)H(3))N(SiMe(3))) can be utilized as an effective synthon for building a variety of multimetallic assemblies containing the Si-O-M motif. The type of metallosiloxane synthesized-its nuclearity and its molecular topology-can be readily modulated by the choice of the metal substrate, reaction stoichiometry, and reaction conditions. It is anticipated that the synthetic principles elaborated here will allow the design of many other multifunctional synthons.

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PubMed2004

Two types of intramolecular addition of an Al-N multiple-bonded monomer LAlNAr' arising from the reaction of LAl with N3Ar' (L = HC[(CMe)(NAr)]2, Ar' = 2,6-Ar2C6H3, Ar = 2,6-iPr2C6H3).

The reaction of beta-diketiminated aluminum(I) monomer LAl with a large bulky azide N3Ar' (L = HC(CMeNAr)2, Ar' = 2,6-Ar2C6H3, Ar = 2,6-iPr2C6H3) in the temperature range from -78 degrees C to room temperature affords two different isomers 2 and 3, which have been characterized by spectroscopic and X-ray structural analyses, as well as elemental analysis. The variable-temperature 1H NMR kinetic studies of this reaction indicate the existence of the monomer LAlNAr' (1) at low temperature and the thermal stability of the compounds increases in the order of 1 < 2 < 3.

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PubMed2004

Metalated hybrid polymers as catalytic reagents for phosphate ester hydrolysis and plasmid modification.

Pendant pyrazolylcyclophosphazene containing hybrid cross-linked polymer (CPPL) has been utilized for binding Zn(II). The metalated polymer (CPPL-Zn) has been found to be very effective catalyst for the hydrolysis of a RNA model phosphodiester substrate [2-(hydroxypropyl)-p-nitrophenyl phosphate, hNPP]. In addition, CPPL-Zn also cleaved supercoiled plasmid DNA pBR322 thus providing a novel structural motif of inorganic-organic hybrid polymers as synthetic nucleases.

Catalysis↗
PubMed2004

Molecular zinc phosphonates: synthesis and X-ray crystal structures of [[(ZnMe)4(THF)2][tBuPO3]2] and [[(ZnEt)3(Zn(THF))3][tBuPO3]4[mu3-OEt]].

The reactions of zinc alkyls with tert-butylphosphonic acid in 2 : 1 and 1 : 1 molar ratios afforded [[(ZnMe)(4-)(THF)2][tBuPO3]2] (2) and [[(ZnEt)3(Zn(THF))3][tBuPO3]4[mu3-OEt]] (3), respectively. Compounds 2 and 3 have been fully characterised by means of spectroscopic and analytical methods. Single-crystal X-ray diffraction studies revealed that zinc phosphonates 2 and 3 are tetra- and hexa-nuclear, respectively. This is in contrast to the dodecanuclear zinc phosphonate [[Zn2(THF)2(ZnEt)6Zn4(mu4-O)][(tBuPO3)8]] (1) obtained in a 1.5 : 1 reaction between zinc alkyls and tBuP(O)(OH)2.

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