Development of robust chiroptical systems through spirobifluorenes.

Chiroptical responses are valuable for the structural determination of dissymmetric molecules. However, the development of everyday applications based on chiroptical systems is yet to come. We have been earlier using axially chiral allenes for the construction of linear, cyclic, and cage-shaped molecules that present remarkable chiroptical responses. Additionally, we have developed chiral surfaces through upstanding chiral architectures. Since the goal is to obtain robust chiroptical materials, more recently we have been studying spirobifluorenes (SBFs), a well-established building block in optoelectronic applications. After theoretical and experimental demonstration, the suitability of chiral SBFs for the development of robust chiroptical systems was certified by the construction all-carbon double helices, flexible shape-persistent macrocycles, chiral frameworks for surface functionalization, and structures featuring helical or spiroconjugated molecular orbitals. Here, we give an overview of our contribution to these matters.

Selective Schiff Base Formation of Group 9 Organometallic Complexes with Functionalized Spirobifluorene Ligands.

Organic amines are important compounds present in a wide variety of products, which makes the development of new systems for their detection an interesting field of study. New organometallic complexes of group 9 [MCp*X(2'-R-2-py-SBF)] (M = Ir, Rh; R = H, X = Cl (6), R = H, X = OAc (7), R = CHO, X = Cl (8)), and [IrCp*Cl(2', 7-diCHO-2-py-SBF)] (9) (Cp* pentamethylcyclopentadienyl, SBF = 9,9'-spirobifluorene) bearing bidentate C-N ligands based on 9,9'-spirobifluorene were obtained and characterized by NMR spectroscopy, mass spectrometry, IR spectroscopy, and X-ray diffraction analysis when possible. The formation of a Schiff base to give complexes with the formula [MCp*Cl(2'-CH=NR-2-py-SBF)] (M = Ir, Rh; R = alkyl or aryl (10-12)), through condensation of an amine, and the aldehyde group present in these new complexes was studied leading to a selective reactivity depending on the nature of the amine and the metal center. While the iridium complexes only react with aromatic amines, the rhodium derivative requires heat for those but can react at room temperature with aliphatic amines.

Optical and electrochemical properties of spirobifluorene iridanaphthalene complexes.

Three new spirobifluorene iridaaromatic compounds bearing electron-withdrawing or electron-donor substituents or another iridanaphthalene moiety have been synthesized and structurally characterized. Thorough experimental and theoretical evaluation revealed that these novel systems present a high thermal, air and electrochemical stability as well as low optical and electronic energy gap values with a significant redshift of the absorption maximum in the UV-Vis spectra and predicted remarkably higher first hyperpolarizabilities compared to their organic counterparts. Therefore, the combination of a metallaaromatic system with a spirobifluorene moiety leads to the design and development of new spirobifluorene derivatives. These new systems have shown interesting optical and electronic properties making them of interest for future applications in optoelectronics.

Key factors in the synthesis of polycyclic iridaaromatics via the methoxyalkenylcarbene pathway.

Polycyclic iridaaromatic compounds are of great interest not only because of the contributions made in "aromatic chemistry", but also because of the possibility of improving the results of the applications of the corresponding organic analogues in different fields. Therefore, understanding the requirements necessary to build on demand this type of compound with specific properties is of great importance. In this work, the keys to successfully synthesize iridaaromatic complexes via methoxyalkenylcarbenes are established. Experimental and theoretical results show (i) that bearing two aromatic substituents on the gamma carbon of the methoxyalkylcarbene promotes the C-H bond activation; (ii) the need for large steric hindrance of the second substituent for a selective synthesis and, (iii) the selectivity in the C-H bond activation towards the less sterically hindered system.

Iridaaromatics via Methoxy(alkenyl)carbeneiridium Complexes.

This review describes the development of a versatile methodology to synthesize polycyclic metallaaromatic hydrocarbons based on iridium, as well as the studies that helped us to determine and understand what is required in order to broaden the scope and the selectivity of the methodology and stabilize the complexes obtained. This methodology aims to open the door to new materials based on graphene fragments.

Spirobifluorene Metallaaromatics.

Spirobifluorene derivatives find use in many end-user applications. Therefore, further expansion of their scope is the focus of many research studies. However, although the optical properties of spirobifluorenes can be greatly tuned through incorporation of metal complexes, to date, spirobifluorene metallaaromatics remain unknown. Taking advantage of the versatility of our methodology for the synthesis of metallaaromatic systems, this work reports the first metallaaromatic spirobifluorene compound. The presence of an Ir atom was found to redshift the absorption maximum by ca. 1.1 eV compared to bare spirobifluorene. Additionally, X-ray analysis as well as anisotropy of the current-induced density calculations revealed this compound to be of aromatic nature. The high stability in solution, solid state, under air, and at high temperature, as well as distinct optical properties of this new class of compounds are expected to open new frontiers for chiroptical and optoelectronic applications.

Counterion-dependent deuteration of pentamethylcyclopentadiene in water-soluble cationic Rh(III) complexes assisted by PTA.

[Cp(*)RhCl(PTA)(2)]X (PTA = 7-phospha-1,3,5-triazaadamantane) undergoes an H/D exchange process between the methyl groups of Cp(*) and D(2)O whose rate depends on the coordinating ability of the counterion X(-). Kinetic studies and DFT calculations indicate that deuteration involves the abstraction of a Me-Cp(*) proton by a coordinated OH(-); the formation of the latter seems to be facilitated by the presence of the N-basic centers of PTA.

NMR studies on the novel heterobimetallic complexes [M(dppm)(Ph(2)PCH(2)PPh(2)PPPP) {Pt(PPh3)2}]OTf (M = Rh, Ir) derived from the stepwise activation of white phosphorus.

The solution structures of the novel heterobimetallic complexes [Ir(dppm)(Ph(2)PCH(2)PPh(2)PPPP){Pt(PPh(3))2}]OTf and [Rh(dppm)(Ph(2)PCH(2)PPh(2)PPPP){Pt(PPh(3))(2)}]OTf derived from the reaction of Rh and Ir--P(5) precursors with [Pt(C2H4)(PPh3)2] have been unambiguously assigned on the basis of 1H NMR and 31P{1H} NMR data. The results are in agreement with the regio-selective insertion of the {Pt(PPh3)2} moiety resulting in a new pentaphosphorus topology which agrees with the formal formation of a unique phosphonium(+)-tetraphosphabutadienide(2-) ligand.