Synthesis, interconversions, and structural characterization of the molybdenum sulfide anions, [(S4)2MoS]2-, [(S4)2MoO]2-, (Mo2S10)2- and (Mo2S12)2-

Draganjac, M.; Simhon, E. D.; Chan, L. T.; Kanatzidis, Mercouri G.; Baenziger, N. C.; Coucouvanis, D.

doi:10.1021/ic00139a014

Cited by 108 publications

(78 citation statements)

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“…Here we report the synthesis, ionization energy (IE) and electron affi nity (EA), and use in doping of P3HT, of Mo(tfd-CO 2 Me) 3 . The dianion of Mo(tfd-CO 2 Me) 3 was isolated as its tetraethylammonium salt from the reaction of methyl 4,4,4-trifl uorobut-2-ynoate) [ 30 ] with (NEt 4 + ) 2 [MoS 9 ] 2− ; [ 31 ] the neutral dopant was obtained after oxidation of the dianion with nitrosonium hexafl uorophosphate. Finally, we create effi cient hole-collection contacts on bulk heterojunction solar cells using this same approach.…”

Section: Are Shown Inmentioning

confidence: 99%

Enhanced Charge‐Carrier Injection and Collection Via Lamination of Doped Polymer Layers p‐Doped with a Solution‐Processible Molybdenum Complex

Dai

Zhou

Shu

et al. 2013

Adv Funct Materials

102

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2197 www.MaterialsViews.com wileyonlinelibrary.comcan be straightforwardly controlled down to a few nanometers by co-evaporation of the host and the dopant molecules. [ 2,4,12,13 ] Carrier injection enhancement of several orders-of-magnitude in organic lightemitting diodes and transistors has been demonstrated. [14][15][16][17][18] Doping-induced enhancement of charge carrier collection at small-molecule organic solar cell contacts has also been demonstrated. [ 12,13,19 ] Achieving the same degree of spatial control of dopant profi le for polymerbased devices is more challenging: polymer fi lms are solution-deposited and, although doped fi lms can be obtained via deposition of a solution containing the host and dopant, spatial distribution of the dopants cannot be easily controlled. Sequential spin-coating of undoped and doped fi lms using orthogonal solvents is one possible approach; however, the polymer-solvent compatibility needed for forming high quality fi lms and interfaces is not assured. We present here a conceptually simple approach based on soft-contact transferlamination (SCTL) of a polymer homojunction, using a soft stamp, for example, polydimethylsiloxane (PDMS), as a transfer medium. SCTL has been extensively used in the past for the deposition of metal electrodes [ 20,21 ] or active layers in organic transistors [ 22,23 ] and photovoltaic cells. [24][25][26][27][28] In the present case, two polymer fi lms, one undoped and one doped, are prepared separately via spin-coating, and then joined via SCTL to realize doped hole-injection or -collection contacts for diodes and solar cells. We have previously demonstrated with two polymers, poly(3-hexylthiophene) (P3HT) ( Figure 1 ) and poly[(9-,9-dioctylfl uorenyl-2,7-diyl)-co-(1,4-benzo-{2,1′-3}-thiadiazole)] (F8BT), that the lamination process of undoped fi lms leads to "transparent" homojunctions, that is, interfaces that are electronically and electrically seamless [ 29 ] as evidenced by the facts that i) no signifi cant energy shift of molecular levels occurs across the SCTL junction, and ii) the current injected from either electrode is independent of whether the middle layer consists of a single polymer fi lm of thickness "t", or of two laminated fi lms with the same total thickness "t' . These results demonstrate that SCTL is a viable method for assembling multilayer polymer devices from separately fabricated layers, thus enabling functionalization, doping, and other materials modifi cation of specifi c parts of a device structure. Though demonstrated to work effectively across metal-metal interfaces, this Poly(3-hexylthiophene) (P3HT) is p-doped by the new soluble dopant molybdenum tris[1-(methoxycarbonyl)-2-(trifl uoromethyl)-ethane-1,2-dithiolene] and investigated via photoemission spectroscopy and transport measurements.Soft-contact transfer lamination of thin layers of the doped P3HT on undoped polymer layers is used to create spatially-confi ned doped regions, which serve as hole-injection contacts on P3HT diodes. This strategy is then used to...

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Section: Are Shown Inmentioning

confidence: 99%

Enhanced Charge‐Carrier Injection and Collection Via Lamination of Doped Polymer Layers p‐Doped with a Solution‐Processible Molybdenum Complex

Dai

Zhou

Shu

et al. 2013

Adv Funct Materials

102

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“…Complexes 1-3 are Mo III , Mo IV and Mo V complexes, respectively, the sulfido ligands adopting increasingly reduced forms along the series; they are interconverted by energetic stimuli such as heat or light [18,19]. Complex (4), isolated from aqueous solutions as the ammonium salt [20], converts into (5) merely upon dissolution in N,N-dimethylformamide (DMF) and addition of NR þ 4 cations [21]. This example underscores the influence of relatively minor perturbations, such as crystal packing forces, solvent properties and ion pairing effects, in metal-sulfur chemistry.…”

Section: Polysulfido Complexesmentioning

confidence: 99%

“…Coucouvanis and coworkers reported that the reaction of (NEt 4 ) 2 (5) anions [21]. The mononuclear species adopt square pyramidal structures with apical chalcogenide ligands and non-planar, bidentate, basal tetrasulfido ligands (Fig.…”

Section: Group 6 Chemistrymentioning

confidence: 99%

Facets of early transition metal–sulfur chemistry: Metal–sulfur ligand redox, induced internal electron transfer, and the reactions of metal–sulfur complexes with alkynes

Young

2007

Journal of Inorganic Biochemistry

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“…In 3 the molybdenum atoms are five‐coordinate rather than six‐coordinate as in 2 and the MoFeCu 2 S 4 cuboidal subunits are “opened‐up” in 3 whereas the MoFe 3 S 4 subunits in 2 are “closed”. The axial and mean equatorial MoS bonds in 3 at 2.227 Å and 2.325 Å, respectively, are not very similar to those in either the [(S 4 ) 2 Mo IV S] 2− complex16 (2.128(1) Å, 2.359 Å) or the SMo V (S 4 ) unit in the [Mo 2 S 10 ] 2− ion17 (2.123 Å, 2.413 Å).…”

mentioning

confidence: 89%

Metal Clusters as Ligands: Substitution of Fe ions in Fe/Mo/S Clusters by Thiophilic Cu^I Ions To Give Clusters with [Cu₄Mo₂Fe₂S₈]⁴⁺ and [Cu₅Mo₃Fe₄S₁₁]⁶⁺ Cores

Koutmos

Coucouvanis

2005

Angewandte Chemie

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Die Reaktivität von Fe/S‐ und Fe/Mo/S‐Clustern, die denen in biologischen Systemen ähneln, gegenüber thiophilen Kupferionen wurde untersucht. Dabei wurden zwei Heteromehrkerncluster mit unterschiedlichen Koordinationsgeometrien im gleichen Molekül erhalten. In beiden liegen FeIII‐, MoV‐ und CuI‐Zentren mit pseudotetraedrischer, pseudooktaedrischer bzw. pseudotrigonaler Koordinationsumgebung vor (siehe Struktur).

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Synthesis, interconversions, and structural characterization of the molybdenum sulfide anions, [(S4)2MoS]2-, [(S4)2MoO]2-, (Mo2S10)2- and (Mo2S12)2-

Cited by 108 publications

References 0 publications

Enhanced Charge‐Carrier Injection and Collection Via Lamination of Doped Polymer Layers p‐Doped with a Solution‐Processible Molybdenum Complex

Enhanced Charge‐Carrier Injection and Collection Via Lamination of Doped Polymer Layers p‐Doped with a Solution‐Processible Molybdenum Complex

Facets of early transition metal–sulfur chemistry: Metal–sulfur ligand redox, induced internal electron transfer, and the reactions of metal–sulfur complexes with alkynes

Metal Clusters as Ligands: Substitution of Fe ions in Fe/Mo/S Clusters by Thiophilic Cu^I Ions To Give Clusters with [Cu₄Mo₂Fe₂S₈]⁴⁺ and [Cu₅Mo₃Fe₄S₁₁]⁶⁺ Cores

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Synthesis, interconversions, and structural characterization of the molybdenum sulfide anions, [(S4)2MoS]2-, [(S4)2MoO]2-, (Mo2S10)2- and (Mo2S12)2-

Cited by 108 publications

References 0 publications

Enhanced Charge‐Carrier Injection and Collection Via Lamination of Doped Polymer Layers p‐Doped with a Solution‐Processible Molybdenum Complex

Enhanced Charge‐Carrier Injection and Collection Via Lamination of Doped Polymer Layers p‐Doped with a Solution‐Processible Molybdenum Complex

Facets of early transition metal–sulfur chemistry: Metal–sulfur ligand redox, induced internal electron transfer, and the reactions of metal–sulfur complexes with alkynes

Metal Clusters as Ligands: Substitution of Fe ions in Fe/Mo/S Clusters by Thiophilic CuI Ions To Give Clusters with [Cu4Mo2Fe2S8]4+ and [Cu5Mo3Fe4S11]6+ Cores

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Metal Clusters as Ligands: Substitution of Fe ions in Fe/Mo/S Clusters by Thiophilic Cu^I Ions To Give Clusters with [Cu₄Mo₂Fe₂S₈]⁴⁺ and [Cu₅Mo₃Fe₄S₁₁]⁶⁺ Cores