Metal Dependence on the Bidirectionality and Reversibility of the Singlet Energy Transfer in Artificial Special Pair-Containing Dyads.

The demetalation of a precursor dyad, 3, built upon a zinc(II)-containing artificial special pair and free-base antenna, leads to a new dyad, 4, for singlet energy transfer composed of cofacial free-base porphyrins (acceptor), [Fb]2 bridged by a 1,4-C6H4 group to a free-base antenna (donor), [Fb]. This dyad exhibits the general structure [M]2-C6H4-[Fb], where [M]2 = [Fb]2, and completes a series reported earlier, where [M]2 = [Mg]2 (2) and [Zn]2 (3). The latter dyads exhibit a bidirectional energy-transfer process at 298 K for 2 and at 77 K for 3. Interestingly, a very scarce case of cycling process is observed for the zinc-containing dyad at 298 K. The newly reported compound 4 exhibits a quasi unidirectional process [Fb]*→[Fb]2 (major, kET = 2 × 1011 s-1 at 298 K), where the remaining is [Fb]2*→[Fb] (minor, kET = 8 × 109 s-1 at 298 K), thus completing all possibilities. The results are analyzed in terms of molecular orbital couplings (density functional theory computations), Förster resonance energy transfer parameters, and temperature dependence of the decay traces. This study brings major insights about artificial special pair-containing dyads and clearly contributes to a better understanding of the communication between the two main components of our models and those already described in the literature.

Design of triads for probing the direct through space energy transfers in closely spaced assemblies.

Using a selective stepwise Suzuki cross-coupling reaction, two trimers built on three different chromophores were prepared. These trimers exhibit a D(^)A1-A2 structure where the donor D (octa-ß-alkyl zinc(II)porphyrin either as diethylhexamethyl, 10a, or tetraethyltetramethyl, 10b, derivatives) through space transfers the S1 energy to two different acceptors, di(4-ethylbenzene) zinc(II)porphyrin (A1; acceptor 1) placed cofacial with D, and the corresponding free base (A2; acceptor 2), which is meso-meso-linked with A1. This structure design allows for the possibility of comparing two series of assemblies, 9a,b (D(^)A1) with 10a,b (D(^)Â1-A2), for the evaluation of the S1 energy transfer for the global process D*→A2 in the trimers. From the comparison of the decays of the fluorescence of D, the rates for through space energy transfer, kET for 10a,b (kET ≈ 6.4 × 10(9) (10a), 5.9 × 10(9) s(-1) (10b)), and those for the corresponding cofacial D(^)A1 systems, 9a,b, (kET ≈ 5.0 × 10(9) (9a), 4.7 × 10(9) s(-1) (9b)), provide an estimate for kET for the direct through space D*→A2 process (i.e., kET(D(^)A1-A2) - kET(D(^)A1) = kET(D*→A2) ∼ 1 × 10(9) s(-1)). This channel of relaxation represents ∼15% of kET for D*→A1.

Is the special pair structure a good strategy for the kinetics during the last step of the energy transfer with the nearest antenna? A chemical model approach.

A cofacial bis(Mg(II)porphyrin)-C(6)H(4)-free base ([Mg(2)]-bridge-FB) dyad shows S(1) energy transfer in both directions and much slower rates than similar monoporphyrin systems are observed.

Acceleration of the through space S1 energy transfer rates in cofacial bisporphyrin bio-inspired models by virtue of substituents effect on the Förster J integral and its implication in the antenna effect in the photosystems.

The singlet k(ET) for cofacial ß-octaalkylporphyrin/bis(meso-aryl)porphyrin dyads increases linearly with the gap between the donor-acceptor 0-0 fluorescence peaks at 77 K.

Rh(I) coordination chemistry of chiral alpha-aminophosphine(eta6-arene)chromium tricarbonyl ligands.

The diastereoselective addition of Ph(2)PH to the chiral ortho-substituted eta(6)-benzaldimine complexes (eta(6)-o-X-C(6)H(4)CH=NAr)Cr(CO)(3) (1, X = MeO, Ar = p-C(6)H(4)OMe; 2, X = Cl, Ar = Ph) leads to the formation of the corresponding chiral aminophosphines (alpha-P,N) Ph(2)P-CH(Ar(1))-NHAr(2) (3, Ar(1) = o-C(6)H(4)(OCH(3))[Cr(CO)(3)], Ar(2) = p-C(6)H(4)OCH(3); 4, Ar(1) = o-C(6)H(4)Cl[Cr(CO)(3)], Ar(2) = Ph) in equilibrium with the starting materials. The uncomplexed benzaldimine (o-ClC(6)H(4)CH=NPh), 2', analogously produces an equilibrium amount of the corresponding aminophosphine Ph(2)P-CH(Ar(1))-NHAr(2) (4', Ar(1) = o-C(6)H(4)Cl, Ar(2) = Ph). Depending on the equilibrium constant, the subsequent addition of (1)/(2) equiv of [RhCl(COD)](2) (COD = 1,5-cyclooctadiene) leads to either Ph(2)PH oxidative addition in the case of 3 or to the corresponding [RhCl(COD)(alpha-P,N)] complexes [RhCl(COD)(Ph(2)P-CH[o-C(6)H(4)Cl[Cr(CO)(3)]]-NHPh)] (5) and [RhCl(COD)(Ph(2)P-CH(o-C(6)H(4)Cl)-NHPh)] (5') in the cases of the aminophosphines 4 and 4'. The addition of the latter ligands, as racemic mixtures, to (1)/(4) equiv of [Rh(CO)(2)Cl](2) leads to the [RhCl(CO)(alpha-P,N)(2)] complexes [RhCO(Ph(2)P-CH[o-C(6)H(4)Cl[Cr(CO)(3)]]-NHPh)(2)Cl] (7) or [RhCO(Ph(2)P-CH(o-C(6)H(4)Cl)-NHPh)(2)Cl] (7') as mixtures of (R(C),S(C))/(S(C),R(C)) and (R(C),R(C))/(S(C),S(C)) diastereomers. The rhodium complexes 5 and 7' have been fully characterized by IR and (31)P NMR spectroscopies and X-ray crystallography. These compounds exhibit intramolecular Rh-Cl.H-N interactions in the solid state and in solution. The stability of the new rhodium complexes has been studied under different CO pressures. Under 1 atm of CO, 5 is converted to an unstable complex [RhCl(CO)(2)(alpha-P,N)], 6, which undergoes ligand redistribution leading to 7 plus an unidentified complex. This reaction is inhibited under higher CO or syngas pressure, as confirmed by the observation of the same catalytic activity in hydroformylation when styrene was added to a catalytic mixture that was either freshly prepared or left standing for 20 h under high CO pressure.

Synthesis, coordination to Rh(I), and hydroformylation catalysis of new beta-aminophosphines bearing a dangling nitrogen group: an unusual inversion of a Rh-coordinated P center.

Variants of the beta-aminophosphine L(1) [Ph(2)PCH(2)CH(Ph)NHPh] containing additional nitrogen donor functions have been prepared. These functions are branched off the C atom adjacent to the P atom, or the P atom itself. Ligand [Ph(2)PCH(o-C(6)H(4)NMe(2))CH(Ph)NHPh] has been obtained as a mixture of two diastereomers L(3A) and L(3B) by lithiation of L(2) [Ph(2)PCH(2)(o-C(6)H(4)NMe(2))] with n-BuLi followed by PhCH=NPh addition and hydrolysis. The diastereomers have been separated by fractional crystallization from ethanol. Ligand Et(2)NCH(2)P(Ph)CH(2)CH(Ph)NHPh has been obtained as a mixture of two diastereomers L(5A) and L(5B)(starting with P-Ph reductive cleavage of L(1) by lithium and subsequent hydrolysis to give PhP(H)CH(2)CH(Ph)NHPh (mixture of two diastereomers L(4A) and L(4B)). The latter reacts with diethylamine and formaldehyde to afford the L(5) diastereomeric mixture. Complexes RhCl(CO)(L) (L = L(3A), 1(A); L(3B), 1(B); L(5A/B), 2(A/B)) were obtained by reaction of [RhCl(CO)(2)](2) and the appropriate ligand or ligand mixture. Complexes 1(A), 1(B), and 2(A) have been isolated in pure form and characterized by classical techniques and by single-crystal X-ray diffraction. All structures exhibit a bidentate kappa-P,kappa-N(NHPh) mode similar to the complex containing L(1). While complexes 1(A) or 1(B) are stable in CDCl(3) solution, complex 2(A) slowly converts to its diastereomer 2(B). This unexpected epimerization appears to take place by inversion at the Rh-coordinated P center, an apparently unprecedented phenomenon. A mechanism based on a reversible P-C bond oxidative addition is proposed. The influence of the pendant nitrogen function of the diaminophosphines L(3A) and L(5A/B) on the rhodium catalytic activity in styrene hydroformylation has been examined and compared to that of the aminophosphines L(1) or L(2). The observed trends are related to the basicity of the dangling amine function and to its proximity to the metal center.