Highly Conductive Halogenated Low-Dimensional Materials

Marks, Tobin J.; Kalina, Davida Webster

doi:10.1007/978-1-4613-3249-7_6

Cited by 72 publications

(40 citation statements)

References 132 publications

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“…We have examined the well-known KI-12-HzO system by Raman spectroscopy to investigate possible pressure dependence of polyiodide speciation reactions. (4,5,9). ~t is also consistent with recent ab …”

Section: Resultsmentioning

confidence: 94%

A Note on the Pressure Dependence of Aqueous Polyiodide Species

Remmele

McMillan

1987

Spectroscopy Letters

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Section: Resultsmentioning

confidence: 94%

A Note on the Pressure Dependence of Aqueous Polyiodide Species

Remmele

McMillan

1987

Spectroscopy Letters

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“…4(a)] andfSiPcO-);;l [ Fig. 4(b)] [61,64]. More direct evidence has recently been presented by Pietro et al [67,68], based upon discrete variation X , studies of the dimeric subunit (HOSiPc-OSiPcOH) of Figure 4 …”

Section: Transfer Without Bridge Assistance: Phthalocyaninesmentioning

confidence: 92%

Intramolecular electron transfer, with bridge assistance and without, in molecules and models

Hale

Ratner

1984

Int. J. Quantum Chem.

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Current experimental efforts, both with isolated binuclear metal complexes and with modified proteins, are focusing on the role of distance and of bridging groups in intramolecular electron transfer. After a brief overview both of standard and nonadiabatic electron transfer rates (in Hopfield's formulation) and of the current experiments, we consider the possibility of bridge-assisted intramolecular electron transfer in three specific situations. For the bridged binuclear transition-metal complexes studied by Taube and his students, the tunneling integral T can be deduced by study of the optical intervalence transfer band. Here we discuss semiempirical calculations which suggest that bridge assistance occurs, and determine the size of T. The assistance is via a superexchangetype mechanism, and we suggest that hole-type or electron-type superexchange should dominate in saturated or unsaturated bridges, respectively. For the very strongly coupled Creutz-Taube ion, involving a pyrazine bridge, the electronic structure study of Ondrechen et al. requires the invoking of a three-site model to understand the optical and EPR data; this involves bridge-assisted transfer with a vengeance. Finally, for an oxide-bridged phthalocyanine dimer, the transfer takes place via ring 71-7~ overlap, and no bridge assistance occurs. Thus bridge assistance in T will depend on the geometry and energetics of the specific case under study. One generally suspects, however, that bridge assistance will be found in very long-range (>6 A) transfer.

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“…For the quantitative analysis of iodine alternatively aluminium was used as the reducing agent. The Raman spectrum (BrukerM ULTIRAMs pectrometer (Nd:YAG-Laser at 1064 nm; RT-InGaAs-detector; backscatteringgeometry))shows twostrongbands at 140and 115cm -1 indicating aslightly asymmetric triiodide anion [5]. …”

mentioning

confidence: 99%

Crystal structure of 3-aminium-pyridin-1-ium bis(triiodide) dihydrate, C5H12I6N2O2

Reiß

Leske

2014

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of material 3-Aminopyridine(0.16 g; 1.7mmol) wasdissolved in 10 ml concentrated hydroiodicacid yielding abrown mixture. This mixture was heated to 90°C and then slowly cooled to room temperature. Within 3-4 days orange needles grew from this solution. Elemental analysis (C 5 H 12 N 2 I 6 O 2 ): Calcd., %: C, 6.72; H, 1.35; N, 3.13; I, 85.21. Found, %: C, 6.83; H, 1.28; N, 3.19; I, 85.02. For details on theelemental analytical methods used, see general procedures giveninthe literature [3,4]. For the quantitative analysis of iodine alternatively aluminium was used as the reducing agent. The Raman spectrum (BrukerM ULTIRAMs pectrometer (Nd:YAG-Laser at 1064 nm; RT-InGaAs-detector; backscatteringgeometry))shows twostrongbands at 140and 115cm -1 indicating aslightly asymmetric triiodide anion [5]. Experimental detailsOne of the water molecules (O2/O2a) is disordered over two sites close to the mirror plane (ratio: 1/1; for clarity only one of the two half occupied positions is shown in the figure). Positional coordinates of hydrogen atomsi nvolved in hydrogen bonds were refined using distance restraints. U iso values for all hydrogen atoms were settoplausible values.The Flackparameter of 0.01(2)was determined using 1624 quotients [(I+)- DiscussionBecause of their biological activity there is ageneral interest in aminopyridines [7]. Especially the monoprotonated cations are known to inactivate K + channels reversibly [8]. Polyiodides are defined as extended ionic structures that fulfill the general formula I (2m+n) n-(n =1-4, m =integer).They are formally built from I -,I 3 -and I 2 units and show astrong tendency to concatenate to extended motifs by halogen halogen interactions [9, 10].Moreover there is afocus on diaminium and pyridinium iodides and corresponding polyiodides, as they have asignificant influence on the redox chemistry in dye-sensitized solar cells [11, 12].In the recent past, several groups have synthesized new polyiodides using stick-shaped cations whose lengths andshapes fit with the structures of the polyiodide anions [13][14][15][16].I np articular, the semi-flexible a,w-diazaniumalkane dicationsh aves uccessfully been used for the synthesis of aseries of new polyiodide salts [4,[17][18][19][20]. Nitrogen based heterocyclic cations are also known to template the synthesis of new polyiodides [21][22][23].This contribution is part of our ongoing interest in the structural chemistry of iodide and polyiodide containing compounds. The asymmetric unit of the title structure is composed of one half of adication, and one half water molecule (O1) both lying on amirror plane; asecond water molecule (O2) appears disordered over two positions near to amirror plane and one triodide anion is located in ageneral position (see figure; ellipsoidsare drawn at the 70 %proba-bility level). All moieties are connected by N-H×××I, O-H×××Iand N-H×××Oh ydrogen bonds whose parameters are in accord with those reported in the literature [24]. Hydrogen bonded subunits are composed of one dication, two anions and two w...

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Highly Conductive Halogenated Low-Dimensional Materials

Cited by 72 publications

References 132 publications

A Note on the Pressure Dependence of Aqueous Polyiodide Species

A Note on the Pressure Dependence of Aqueous Polyiodide Species

Intramolecular electron transfer, with bridge assistance and without, in molecules and models

Crystal structure of 3-aminium-pyridin-1-ium bis(triiodide) dihydrate, C5H12I6N2O2

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