Unprecedented conformational modulation of the efficiency of luminescence in Ru(II) bipyridyl complexes containing a bis(bidentate) phosphine

Gutmann, Rene; Czermak, Georg; Dumfort, Alexander; Veer, Wytze E. van der; Hong, Bo; Kopacka, Holger; Ongania, Karl‐Hans; Bechtold, Thomas; Brüggeller, Peter

doi:10.1016/j.inoche.2005.01.009

Cited by 13 publications

(32 citation statements)

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“…The analogous contacts between the phenyl rings along a trans axis of the cyclobutane rings are 3.022 Å in 1 and 3.024 Å in 3. These contact approaches are indicative of high ''steric pressure'' [4,13]. Interestingly, neither a different diastereoisomeric form nor different polymorphs essentially change this ''steric pressure''.…”

mentioning

confidence: 98%

“…This approach necessarily involves a stepwise sequence of reactions with penalties for yields of less than 100% at each step, which can greatly diminish overall yields in multistep syntheses [3]. Therefore, a photochemical approach would be very interesting, showing simultaneous covalent bond formation and regiospecific modification of chromophores in one step.The use of phosphines leading to enhanced ''steric pressure'' has made it possible to obtain long-lived excited RuP 2 N 4 type units at ambient temperature [4]. The control of the energetic and geometric factors allows the mechanistic study of photoinduced processes, the manipulation of their rates, and finally the control of factors to build up photochemical molecular devices [2].…”

mentioning

confidence: 99%

“…The use of phosphines leading to enhanced ''steric pressure'' has made it possible to obtain long-lived excited RuP 2 N 4 type units at ambient temperature [4]. The control of the energetic and geometric factors allows the mechanistic study of photoinduced processes, the manipulation of their rates, and finally the control of factors to build up photochemical molecular devices [2].…”

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confidence: 99%

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Switching on the photochemical reactivity in heterodimetallic OsII–RuII bipyridyl complexes containing a bis(bidentate) phosphine

Gutmann¹,

Eller²,

Fessler³

et al. 2007

Inorganic Chemistry Communications

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confidence: 98%

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confidence: 99%

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Switching on the photochemical reactivity in heterodimetallic OsII–RuII bipyridyl complexes containing a bis(bidentate) phosphine

Gutmann¹,

Eller²,

Fessler³

et al. 2007

Inorganic Chemistry Communications

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“…[12,15] The monometallic precursor complex [Ru(bpy) 2 -(dppcb)](PF 6 ) 2 [2] smoothly reacts with [NiBr 2 (DME)] to give the heterodimetallic species [Ru(bpy) 2 (dppcb)-NiBr 2 ](PF 6 ) 2 (1) in good yield (Scheme 1). The single-crystal X-ray structure of 1 (Figure 1) clearly reveals its diastereotopicity [17] and, hence, 1 also shows four distinct 31 P{ 1 H} NMR signals in solution. Furthermore, in the solid state its single-crystal X-ray structure (vide infra) and the corresponding elemental analyses were obtained.…”

Section: Synthesis Of the Complexes And Solution Investigationsmentioning

confidence: 99%

“…Ru (1) (18) Furthermore, it is important to study the "steric pressure" in 1 and 2Ј, [2,6,17] as nonradiative decay for these RuN 4 P 2 chromophores is typically dominated by energy loss into a series of medium frequency ring-stretching vibrations with energy spacings between 1000 and 1600 cm -1 . [19] The shortest intramolecular contacts between a bpy ligand and a phenyl ring are 2.308 Å in 1 and 2.264 and 2.271 Å for the Ru(1) and Ru(2) moieties in 2Ј, respectively.…”

Section: Crystal Structures Of [Ru(bpy) 2 (Dppcb)nibr 2 ](Pf 6 ) 2 (1mentioning

confidence: 99%

Versatile Supramolecular Coordination Behaviour of a Bis(bidentate) Tetraphosphane

et al. 2013

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The bis(bidentate) phosphane cis,trans,cis-1,2,3,4-tetrakis-(diphenylphosphanyl)cyclobutane (dppcb) has been used for the synthesis of supramolecular complexes, so-called dyads and triads. Depending on the monometallic precursor compound [Ru(bpy) 2 (dppcb)](PF 6 ) 2 or [Ru(bpy) 2 (cis-dppcbO 2 )]-(PF 6 ) 2 [bpy = 2,2Ј-bipyridine, cis-dppcbO 2 = cis,trans,cis-1,2bis(diphenylphosphanoyl)-3,4-bis(diphenylphosphanyl)cyclobutane], [Ru(bpy) 2 (dppcb)NiBr 2 ](PF 6 ) 2 (1) or ΔΛ/ΛΔ-[{Ru(bpy) 2 (cis-dppcbO 2 )} 2 NiBr](PF 6 ) 5 (2) is exclusively formed in good yield by reaction with [NiBr 2 (DME)] (DME = dimethoxyethane). The versatile coordination behaviour of dppcb compared with that of cis-dppcbO 2 is confirmed by cis,trans,cis-2,3-bis(diphenylphosphanoyl)-1,4-bis(diphenylphosphanyl)cyclobutane (2,3-trans-dppcbO 2 , 4). Although two dppcb ligands coordinated simultaneously to a Pd II centre cannot produce a square-planar PdP 4 core, the reaction of two equivalents of 4 with [Pd(CH 3 CN) 4 ](BF 4 ) 2 exclusively leads to meso-(MMMP/MPPP)-[Pd(2,3-trans-dppcbO 2 -[a] 5122 trans-dppcbO 2 , 4) [11] in isolated form with palladium(II) was also investigated (Scheme 2). Usually, it is not possible to combine two dppcb ligands with one palladium(II) centre to generate a square-planar PdP 4 core. [12] However, two equivalents of 4 and one equivalent of [Pd(CH 3 CN) 4 ]-(BF 4 ) 2 exclusively produce meso-(MMMP/MPPP)-[Pd(2,3trans-dppcbO 2 -P,PЈ) 2 ](BF 4 ) 2 (3), which has this square-Eur. J. Inorg. Chem. 2013, 5121-5132

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The Influence of Steric Pressure on the Structure of Homodimetallic Rhodium(I) and Iridium(I) Complexes Containing a Bis(bidentate) Phosphane Ligand

et al. 2007

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P{ 1 H}), mass spectrometry, IR spectroscopy, elemental analyses and melting points. Furthermore, the solid-state structures of seven of these new compounds were fully determined by single-crystal X-ray diffraction analyses to study the influence of steric pressure. The precursor complex [Rh 2 (η 4 -cod) 2 (dppcb)]X 2 (1), X -= BF 4 -, PF 6 -, SbF 6 -, completely characterized by its X-ray structure, smoothly reacts with mono-or bidentate ligands containing phosphorus or nitrogen donor atoms. Thus, monophosphanes and monophosphites produce compounds of the structure type [Rh 2 L 4 (dppcb)](SbF 6 ) 2 [L = PMe 2 Ph, 2; PMePh 2 , 3; P(OMe) 3 , 5; P(OPh) 3 , 6]. The X-ray structures of 3 and 6 show that PMePh 2 and P(OPh) 3 are capable of compensating steric interactions. The treatment of 1 with diphosphanes leads to the structure type [Rh 2 L 2 (dppcb)](SbF 6 ) 2 [L = bis(diphosphanyl)-methane, dppm, 7; bis(diphenylphosphanyl)amine, dppam, 8; 1,2-bis(diphenylphosphanyl)ethane, dppe, 9; cis-1,2-

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Unprecedented conformational modulation of the efficiency of luminescence in Ru(II) bipyridyl complexes containing a bis(bidentate) phosphine

Cited by 13 publications

References 17 publications

Switching on the photochemical reactivity in heterodimetallic OsII–RuII bipyridyl complexes containing a bis(bidentate) phosphine

Switching on the photochemical reactivity in heterodimetallic OsII–RuII bipyridyl complexes containing a bis(bidentate) phosphine

Versatile Supramolecular Coordination Behaviour of a Bis(bidentate) Tetraphosphane

The Influence of Steric Pressure on the Structure of Homodimetallic Rhodium(I) and Iridium(I) Complexes Containing a Bis(bidentate) Phosphane Ligand

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