Browsing by Author "Bhadbhade, MM"

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    2D cobalt based coordination polymer constructed from benzimidazole and acetate ion exhibiting spin-canted antiferromagnetism
    (Royal Society of Chemistry, 2010-05-07) Arai, L; Nadeem, MA; Bhadbhade, MM; Stride, JA
    A coordination polymer, [CoII(bIM)(acetate)] (bIM = benzimidazole) was synthesized using a solvothermal method; the complex has a two dimensional non-interpenetrated network structure and exhibits a spin-canted antiferromagnetic behaviour at low temperature and a high coercive field. © 2010, Royal Society of Chemistry
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    Anomalous structural evolution and glassy lattice in mixed‐halide hybrid perovskites
    (Wiley, 2022-05) Shahrokhi, S; Dubajic, M; Dai, ZZ; Bhattacharyya, S; Mole, RA; Rule, KC; Bhadbhade, MM; Tian, R; Mussakhanuly, N; Guan, X; Yin, Y; Nielsen, MP; Hu, L; Lin, CH; Chang, SLY; Wang, DY; Kabakova, IV; Conibeer, G; Bremner, S; Li, XG; Cazorla, C; Wu, T
    Hybrid halide perovskites have emerged as highly promising photovoltaic materials because of their exceptional optoelectronic properties, which are often optimized via compositional engineering like mixing halides. It is well established that hybrid perovskites undergo a series of structural phase transitions as temperature varies. In this work, the authors find that phase transitions are substantially suppressed in mixed‐halide hybrid perovskite single crystals of MAPbI3‐xBrx (MA = CH3NH3+ and x = 1 or 2) using a complementary suite of diffraction and spectroscopic techniques. Furthermore, as a general behavior, multiple crystallographic phases coexist in mixed‐halide perovskites over a wide temperature range, and a slightly distorted monoclinic phase, hitherto unreported for hybrid perovskites, is dominant at temperatures above 100 K. The anomalous structural evolution is correlated with the glassy behavior of organic cations and optical phonons in mixed‐halide perovskites. This work demonstrates the complex interplay between composition engineering and lattice dynamics in hybrid perovskites, shedding new light on their unique properties. © 2022 The Authors. Small published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
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    Controlled synthesis of isomorphous coordination polymers via in situ ligand transformation reaction: crystal structure, thermal and magnetic properties
    (American Chemical Society, 2010-09) Nadeem, MA; Bhadbhade, MM; Bircher, R; Stride, JA
    A series of isomorphous [M2(ip)2(L)2]n (M = Co, Ni; ip = isophthalate; L = 4,4′-dipyridyl and pyrazine) coordination polymers was synthesized via in situ ligand transformation reactions, in which 1,2,3-benzene tricarboxylic acid (1,2,3-btcH3) undergoes decarboxylation to isophthalate (ip), which was found to be highly dependent on the reaction temperature. The polymers crystallize in the same crystal triclinic system P. The magnetic properties were investigated by a Quantum Design physical property measurement system (PPMS); all four compounds feature almost isostructural M(II) dimers having ferromagnetic (FM) interactions. The interdimer interactions mediated by two different carboxylate groups of ip are weak, while there is no significant magnetic exchange via the 4,4′-dipyridyl ligands along the chain direction. However, substitution with pyrazine leads to antiferromagnetic exchange of nearest neighbor dimers. © 2010, American Chemical Society
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    Coordination polymers of perylenetetracarboxylate with Cs(I) ions: 3D structures with 2D inorganic layers or triple coordination nets
    (Elsevier B. V., 2023-02) Nguyen, TH; Karatchevtseva, I; Bhadbhade, MM; Zhang, YJ
    The self-assembly of perylenetetracarboxylate (ptc) with Cs(I) ions at ambient temperature has been investigated with two coordination polymers being synthesized and structurally characterized. The diffusion of ethanol into a Cs-ptc solution led to the formation of compound 1 [(Cs4(ptc)(H2O)5·nH2O] displaying a compact three-dimensional (3D) structure constructed with 2D undulating layers of Cs polyhedra linked by ptc ligands in two types coordination modes. Extensive π···π interactions among stacking ptc ligands formed large hydrophobic organic channels between the inorganic layers. The addition of ethylenediamine (ED) to the reaction system afforded the formation of compound 2 [(H2ED)5Cs2(ptc)3(H2O)10] showing triple 2D coordination nets with protonated ethylene diammonium cations hydrogen-bonded to both non-bonded carboxyl oxygen and coordinated water molecules. The triple 2D nets are further linked via hydrogen bonding to form a 3D structure. The optical absorption, band gap analysis, vibrational modes and thermal stability of compound 1 were also investigated. Overall, the structural diversity was achieved in the studied self-assembly system at ambient temperature through varying Cs to ptc ratios by introducing ethylene diammonium as a non-metal cation. © 2023 Elsevier B.V.
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    Dysprosium complexes with mono-/di-carboxylate ligands—from simple dimers to 2D and 3D frameworks
    (Elsevier, 2014-11-01) Zhang, YJ; Bhadbhade, MM; Scales, N; Karatchevtseva, I; Price, JR; Lu, KT; Lumpkin, GR
    Four dysprosium (Dy) single carboxylates, a formate, a propionate, a butyrate and an oxalate have been synthesized and structurally characterized. The structure of Dy(HCO2)3 (1) contains nine-fold coordinated Dy polyhedra in perfect tricapped trigonal prisms. They are linked through trigonal O atoms forming 1D pillars which are further linked together through tricapped O atoms into a 3D pillared metal organic framework. The network structure is stable up to 360 °C. The structure of [Dy2(C2O4)3(H2O)6]·2.5H2O (2) contains nine-fold coordinated Dy polyhedra linking together through μ2-bridging oxalate anions into a 2D hexagonal layered structure. Both [Dy2(Pr)6(H2O)4]·(HPr)0.5 (3) [Pr=(C2H5CO2)−1] and [Dy2(Bu)6(H2O)4] (4) [Bu=(C3H7CO2)−1] have similar di-nuclear structures. The Raman vibration modes of the complexes have been investigated. © 2016 Elsevier B.V.
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    Efficient access to chromeno[4,3-b]quinolines related to dependensin
    (© Georg Thieme Verlag Stuttgart, 2017-08-08) Dobrowolski, JC; Fraser, BH; Bhadbhade, MM; Black, DS; Kumar, N
    We report a robust synthesis of novel chromeno[4,3-b]quinoline derivatives structurally similar to the natural product dependensin. The target compounds are accessed through the acid-catalysed condensation of 2-aminoacetophenones or 2-aminochalcones with substituted flavanones, which are in turn obtained from 2-hydroxyacetophenones and benzaldehydes. © 2017 Georg Thieme Verlag Stuttgart
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    Evaluation of the antidepressant therapeutic potential of isocyanine and pseudoisocyanine analogues of the organic cation decynium-22
    (Elsevier B. V., 2017-09-08) Krause-Heuer, AM; Fraser-Spears, R; Dobrowolski, JC; Ashford, ME; Wyatt, NA; Roberts, MP; Gould, GG; Cheah, WC; Ng, CKL; Bhadbhade, MM; Zhang, B; Greguric, I; Wheate, NJ; Kumar, N; Koek, W; Callaghan, PD; Daws, LC; Fraser, BH
    Antidepressant-like activity Herein we describe the synthesis and evaluation of antidepressant properties of seven analogues (1–7) of the low affinity/high capacity transporter blocker decynium-22 (D-22). All analogues (1–7) were synthesized via base promoted coupling reactions between N-alkylated-2-methylquinolinium iodides or N-alkylated-4-methylquinolinium iodides and electrophilic N-alkylated-2-iodoquinolinium iodides. All final compounds were purified by re-crystallization or preparative HPLC and initial evaluation studies included; 1) screening for in vitro α1-adrenoceptor activity (a property that can lead to unwanted side-effects), 2) measuring antidepressant-like activity in a mouse tail suspension test (TST), and 3) measuring effects upon mouse locomotion. The results showed some analogues have lower affinities at α1-adrenoceptors compared to D-22 and showed antidepressant-like activity without the need for co-administration of SSRIs. Additionally, many analogues did not affect mouse locomotion to the same extent as D-22. Plans for additional evaluations of these promising analogues, including measurement of antidepressant-like activity with co-administration of selective serotonin re-uptake inhibitors (SSRIs), are outlined. © 2017 Elsevier B.V.
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    Four new coordination polymers constructed from benzene tricarboxylic acid: synthesis, crystal structure, thermal and magnetic properties
    (Royal Society of Chemistry, 2010-11-07) Nadeem, MA; Bhadbhade, MM; Stride, JA
    The use of 1,3,5-benzene tricarboxylic acid (H3btc) as an organic linker has allowed us to achieve the rational design of two pairs of isostructural coordination polymers having molecular formulae [M2(btc)(F)]n (M(II) = Mn (1), Co (2)) and [M3(btc)(Hbtc)(OH)(H2O)11]n (M(II) = Fe (3), Co (4)) where btc and Hbtc represent the fully and doubly de-protonated tricarboxylates respectively. These compounds were synthesized using hydrothermal methods and characterized by thermal analysis and variable temperature magnetic measurements. The X-ray analysis reveals that compounds 1 and 2 crystallize in the monoclinic space group C2/c while compounds 3 and 4 crystallize in the monoclinic space group C2. Compounds 1 and 2 feature fluoride bridged 1D metal chains linked together via carboxylate groups of btc, whilst compounds 3 and 4 consist of 1D zigzag chains having strong hydrogen bonds with neighbouring chains. Variable temperature magnetic measurements show an overall antiferromagnetic behaviour for compounds 1, 2 and 4, with no indication of magnetic ordering phenomena in the temperature range from 300–2 K. As 3 and 4 are isostructural, we assume that the magnetic properties are similar. © 2010, Royal Society of Chemistry
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    A general and efficient synthesis of 5,6-dihydrodibenzo[b,h][1,6]naphthyridine derivatives
    (Elsevier B. V., 2016-12-07) Dobrowolski, JC; Katen, A; Fraser, BH; Bhadbhade, MM; Black, DS; Kumar, N
    A two-step procedure for the synthesis of dihydrodibenzonaphthyridine derivatives from benzaldehydes and 2-aminoacetophenones, proceeding through a substituted dihydroquinolone intermediate, is described. The synthetic protocol allows for a versatile and robust coupling method between a range of 2-aminoacetophenones or 2-aminobenzophenones and a selection of substituted dihydroquinolones. © 2016 Elsevier B.V.
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    A general synthesis of 7-Phenyl-7,13-dihydro-8H-benzo[6,7]azepino[3,2-c]quinolin-8-ones
    (Thieme, 2019-02-13) Dobrowolski, JC; Nguyen, DHT; Fraser, BH; Bhadbhade, MM; Black, DS; Kumar, N
    Complex benzazepinoquinolone scaffolds can be accessed from the reaction of 2-aminoacetophenones and oxindole derivatives and feature the seven-membered azepine ring moiety commonly found in a range of drug molecules. The described reaction is generally applicable and allows for rapid access to a diverse range of new structures with further potential to build more elaborate molecules. © 2021 Georg Thieme Verlag KG
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    A general synthesis of benzoazepinoindoles – a new class of heterocycles
    (Thieme, 2019-10-09) Dobrowolski, JC; Nguyen, DHT; Fraser, BH; Bhadbhade, MM; Black, DS; Kumar, N
    A new class of heterocyclic compounds, namely the benzoazepinoindolones, has been synthesised through a base-catalysed cyclisation reaction of 1,4-bis(2-aminophenyl)-2-phenylbutane-1,4-dione derivatives and features the prominent seven-membered azepine ring moiety. This synthesis has considerable scope for the rapid generation of more complex structures and is inexpensive and generally applicable. © 2019 Georg Thieme Verlag
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    Guest removal and external pressure variation induce spin crossover in halogen-functionalized 2-D Hofmann frameworks
    (American Chemical Society, 2020-09-27) Brennan, AT; Zenere, KA; Brand, HEA; Price, JR; Bhadbhade, MM; Turner, GF; Moggach, SA; Valverde-Muñoz, FJ; Real, JA; Clegg, JK; Kepert, CJ; Neville, SM
    The effect of halogen functionalization on the spin crossover (SCO) properties of a family of 2-D Hofmann framework materials, [Fe(II)Pd(CN)4(thioX)2]·2H2O (X = Cl and Br; thioCl = (E)-1-(5-chlorothiophen-2-yl)-N-(4H-1,2,4-triazol-4-yl)methanimine) and thioBr = (E)-1-(5-bromothiophen-2-yl)-N-(4H-1,2,4-triazol-4-yl)methanimine)), is reported. Inclusion of both the chloro- and bromo-functionalized ligands into the Hofmann-type frameworks (1Cl·2H2O and 2Br·2H2O) results in a blocking of spin-state transitions due to internal chemical pressure effects derived by the collective steric bulk of the halogen atoms and guest molecules. Cooperative one-step SCO transitions are revealed by either guest removal or the application of external physical pressure. Notably, removal of solvent water reveals a robust framework scaffold with only marginal variation between the solvated and desolvated structures (as investigated by powder and single crystal X-ray diffraction). Yet, one-step complete SCO transitions are revealed in 1Cl and 2Br with a transition temperature shift between the analogues due to various steric, structural, and electronic considerations. SCO can also be induced in the solvated species, 1Cl·2H2O and 2Br·2H2O, with the application of physical pressure, revealing a complete one-step SCO transition above 0.62 GPa (as investigated by magnetic susceptibility and single crystal X-ray diffraction measurements). © 2020 American Chemical Society
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    Hierarchical spin-crossover cooperativity in hybrid 1D chains of Fe(II)-1,2,4-triazole trimers linked by [Au(CN)2]− bridges
    (John Wiley & Sons, Inc, 2021-02-04) Ezzedinloo, L; Zenere, KA; Xie, Z; Ahmed, M; Scottwell, S; Bhadbhade, MM; Brand, HEA; Clegg, JK; Hua, C; Sciortino, NF; Parker, LC; Powell, BJ; Kepert, CJ; Neville, SM
    Foremost, practical applications of spin-crossover (SCO) materials require control of the nature of the spin-state coupling. In existing SCO materials, there is a single, well-defined dimensionality relevant to the switching behavior. A new material, consisting of 1,2,4-triazole-based trimers coordinated into 1D chains by [Au(CN)2]− and spaced by anions and exchangeable guests, underwent SCO defined by elastic coupling across multiple dimensional hierarchies. Detailed structural, vibrational, and theoretical studies conclusively confirmed that intra-trimer coupling was an order of magnitude greater than the intramolecular coupling, which was an order of magnitude greater than intermolecular coupling. As such, a clear hierarchy on the nature of elastic coupling in SCO materials was ascertained for the first time, which is a necessary step for the technological development of molecular switching materials. © 2021 Wiley-VCH GmbH
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    Kinetics vs. thermodynamics: a unique crystal transformation from a uranyl peroxo-nanocluster to a nanoclustered uranyl polyborate
    (Royal Society of Chemistry, 2014-07-30) Zhang, YJ; Bhadbhade, MM; Price, JR; Karatchevtseva, I; Collison, D; Lumpkin, GR
    A novel method to prepare a nano-clustered uranyl polyborate in aqueous solution at room temperature has been developed. The initially formed kinetically favoured sodium uranyl peroxide yellow crystals transform, in the presence of boric acid, to the thermodynamically stable sodium uranyl polyborate in light yellow-green single crystal form. © Royal Society of Chemistry 2016
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    Neodymium coordination polymers with propionate, succinate and mixed succinate–oxalate ligands: synthesis, structures and spectroscopic characterization
    (Elsevier, 2015-12-14) Scales, N; Zhang, YJ; Bhadbhade, MM; Karatchevtseva, I; Kong, L; Lumpkin, GR; Li, F
    Three neodymium (Nd) coordination polymers with propionate, succinate and mixed succinate–oxalate ligands have been synthesized and structurally characterized. Nd2(C3H5O2)6(H2O)3·3H2O (1) has a 1D polymeric structure built with both ninefold and ten-fold coordinated neodymium polyhedra linked through μ2-bridging propionate ligands. Nd2(C4H4O4)3(H2O)2 (2) has a 3D polymeric structure constructed with two distinct ninefold coordinated neodymium polyhedra linked through three types of succinate ligands, two in μ4- and one in μ3-coordination modes. Nd2(C4H4O4)2(C2O4)(H2O)4·3H2O (3) is built with two types of ten-fold coordinated neodymium polyhedra linked through μ4-succinate ligands into 2D undulating layers which are further connected through μ2-oxalate ligands forming a 3D network with channels. Their vibrational modes and thermal stabilities have been further investigated. Crown Copyright © 2015 Published by Elsevier Ltd.
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    Solvothermal synthesis of uranium(VI) phases with aromatic carboxylate ligands: a dinuclear complex with 4-hydroxybenzoic acid and a 3D framework with terephthalic acid
    (Elsevier B.V., 2016-02-01) Zhang, YJ; Karatchevtseva, I; Bhadbhade, MM; Tran, TT; Aharonovich, I; Fanna, DJ; Shepherd, ND; Lu, KT; Li, F; Lumpkin, GR
    With the coordination of dimethylformamide (DMF), two new uranium(VI) complexes with either 4-hydroxybenzoic acid (H2phb) or terephthalic acid (H2tph) have been synthesized under solvothermal conditions and structurally characterized. [(UO2)2(Hphb)2(phb)(DMF)(H2O)3]·4H2O (1) has a dinuclear structure constructed with both pentagonal and hexagonal bipyramidal uranium polyhedra linked through a µ2-bridging ligand via both chelating carboxylate arm and alcohol oxygen bonding, first observation of such a coordination mode of 4-hydroxybenzoate for 5 f ions. [(UO2)(tph)(DMF)] (2) has a three-dimensional (3D) framework built with pentagonal bipyramidal uranium polyhedra linked with µ4-terephthalate ligands. The 3D channeled structure is facilitated by the unique carboxylate bonding with nearly linear C–O–U angles and the coordination of DMF molecules. The presence of phb ligands in different coordination modes, uranyl ions in diverse environments and DMF in complex 1, and tph ligand, DMF and uranyl ion in complex 2 has been confirmed by Raman spectroscopy. In addition, their thermal stability and photoluminescence properties have been investigated. © 2015 Elsevier Inc.
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    Spectroscopic studies and crystal structures of double thorium(IV) oxalates with sodium ions
    (John Wiley and Sons, 2013-11-08) Zhang, YJ; Bhadbhade, MM; Karatchevtseva, I; Gao, J; Price, JR; Lumpkin, GR
    Two new double thorium oxalates with sodium ions have been prepared and characterized by using scanning electron microscopy/energy-dispersive spectroscopy (SEM/EDS), Raman spectroscopy and single-crystal X-ray diffraction. The crystal structure of Na4[Th(C2O4)4]·5.5H2O (1) contains infinite chains, [Th(μ2-C2O4)2(C2O4)3]n4n–, with three terminating bidentate and two bridging tetradentate oxalate ligands. The crystal structure of Na10[Th2(C2O4)9]·15H2O (2) comprises unique dimers, [Th2(μ2-C2O4)(C2O4)8]10–, with Th atoms being coordinated by five oxalato ligands, four terminating bidentate and one bridging tetradentate. The structure is the first dimer of tetravalent actinide oxalato complexes. The spectroscopic results are in good agreement with the crystal structures. © 2013, Wiley-Vch Verlag.
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    Synthesis and characterisation of new tripodal lanthanide complexes and investigation of their optical and magnetic properties
    (Royal Society of Chemistry, 2017-08-21) Craze, AR; Huang, XD; Etchells, I; Zheng, LM; Bhadbhade, MM; Marjo, CE; Clegg, JK; Moore, EG; Avdeev, M; Lindoy, LF; Li, F
    This paper presents the synthesis of a tripodal ligand (H3L) via the Schiff base condensation of N,N-diethylsalicylaldehyde and tris(2-aminoethyl)amine. The neutral complexes of type [EuL], [GdL] and [DyL] were synthesized and characterized by FT-IR, SEM-EDS, PXRD, single crystal X-ray diffraction, CHN analysis and high resolution ESI-MS. X-ray crystallographic studies demonstrated that the heptadentate ligand incorporating a cavity pre-organized by hydrogen bonding binds the Ln(III) ions to yield a face capped octahedral coordination geometry with three-fold symmetry. Photoluminescence studies show a typical Ln(III) absorption character for the three complexes, with [EuL] demonstrating considerably stronger lanthanide-based luminescence peaks, and a Eu(III) centered luminescence lifetime of 0.144 ± 0.01 ms. Temperature/field-dependent DC and temperature/frequency-dependent AC magnetic measurements carried out for the Dy(III) complex indicated obvious magnetic anisotropy and suggested slow relaxation behaviour with considerable quantum tunnelling of the magnetization contribution. © The Royal Society of Chemistry 2017
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    Thorium(IV) and uranium(IV) complexes with cucurbit[5]uril
    (American Chemical Society, 2018-06-27) Zhang, YJ; Bhadbhade, MM; Avdeev, M; Price, JR; Karatchevtseva, I; Li, Q; Tao, Z; Wei, G
    Tetravalent thorium and uranium complexes with cucurbit[5]uril (Q[5]) were investigated with eight new complexes being synthesized and structurally characterized. [Th(Q[5])(OH)(H2O)2]6·18NO3·nH2O (1) has a hexagonal nanowheel structure with each of the six Th4+ ions being cap-coordinated by a Q[5] and monodentate-coordinated to the nearby Q[5]. [Th(Q[5])(HCOO)(H2O)4][Th(NO3)5(H2O)2]2[Th(NO3)3(HCOO)(H2O)2]0.5·NO3·nH2O (2) has a heteroleptic mononuclear structure with a Th4+ ion cap-coordinated on one side of the Q[5] portal and monodentate-coordinated to a formate anion inside the Q[5] cavity. [KTh1.5(Q[5])Cl(NO3)3][Th(NO3)5(H2O)2]·2NO3·2.5H2O (3) has a heterometallic structure with both Th4+ and K+ ions each occupying one side of the two Q[5] portals forming a capsule. [CsTh(Q[5])Cl(NO3)2(H2O)3]·2NO3·nH2O (4) has a heterometallic 1D polymeric structure with both Th4+ and Cs+ ions each occupying one side of the two Q[5] portals, forming monomers which are linked together by sharing two water molecules and one carbonyl oxygen atom between Th4+ and Cs+ ions. [Th(Q[5])Cl(H2O)][CdCl3][CdCl4]·0.5HCl·4H2O (5), [Th(Q[5])Cl(H2O)][Ru2OCl9(H2O)]·0.5HCl·9.5H2O (6), [Th(Q[5])Cl(H2O)][IrCl6]1.5·3H2O (7), and [U(Q[5])Cl(H2O)][ZnCl3(H2O)][(ZnCl4)]·8H2O (8) have similar 1D polymeric structures with Th4+/U4+ ions cap-coordinated on one side of a Q[5] and bidentate coordinated to the nearby Q[5]. The transition metal chlorides act as anions for charge compensation as well as structure inducers via cation–anion interactions forming various anion patterns around the 1D polymers. Actinide contraction has been observed in the early actinide series. © 2018 American Chemical Society
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    Three isolated structural motifs in one crystal: penetration of two 1D chains through large cavities within 2D polymeric sheets
    (Royal Society of Chemistry, 2010-05) Nadeem, MA; Bhadbhade, MM; Bircher, R; Stride, JA
    An unprecedented architecture comprising of three isolated coordination polymers within the same crystalline structure has been obtained, in which two independent infinite one dimensional polymer chains, Cu(bpy)(H2O), fill the voids generated by a third, two dimensional, host framework, Cu3(Hbtc)(btc)(bpy)2. © 2010, Royal Society of Chemistry