Liquid Crystalline Magneto-Optically Active Peralkylated Azacoronene.

Organic Faraday rotators have gained significant attention in recent years as a promising alternative to traditional inorganic magneto-optical (MO) materials as a result of their lower cost, superior mechanical properties, and potential for large-scale deployment. This interest is peaked by the fact that a number of high symmetry, rigid, strongly optically absorbing organic chromophores display Verdet constants an order of magnitude higher than commercial inorganic Faraday rotators. Critical to the development of new generations of organic materials is the ability to organize them in optimal structures for optical coupling/measurements. We report herein the synthesis of a dodecyl-substituted hexapyrrolohexaazacoronene (C12-HPHAC) displaying discotic liquid crystalline (LC) properties and large Faraday rotation. Thin films with a redox mixed C12-HPHAC/C12-HPHAC+2 composition display a discotic columnar LC phase, are stable to air and moisture in the solid and solution states, and achieve a maximum Verdet constant of 3.36 × 105 deg T-1 m-1 at 700 nm. This result is consistent with Serber's model of magnetic circular birefringence and displays one of the largest reported Verdet constants for organic materials in the UV-Vis range. The LC phase aligns the molecules and leads to gains in Verdet constants of up to 105% through the favorable orientation of the molecules' magnetic and electric transition dipole moments with respect to the applied magnetic field.

C-Term Faraday Rotation in Low Symmetry tert-Butyl Substituted Polyferroceniums.

Molecular thin films are currently being investigated as candidate materials to replace conventional atomistic inorganic crystal-based Faraday rotators. High symmetry paramagnetic species have been reported to exhibit large Verdet constants via magnetic field splitting of degenerate ground states. However, lower symmetry open-shell species have not been extensively studied. Herein, we report the Faraday rotation of two poly di-tert-butylferroceniums with diphenylsilane and vinylene linkers. Thin films of oxidized poly[(1,1'-di-tert-butylferrocenyl)diphenylsilane] [poly(tBu2fc-SiPh2)] displayed a 30% increase in maximum Verdet constant relative to the previously reported decamethylferrocenium/PMMA composite, with Verdet constants of -4.52 × 104 deg T-1 m-1 at 730 nm and 4.46 × 104 deg T-1 m-1 at 580 nm. When a sp2-type linker was used, as with the oxidized poly(1,1'-di-tert-butyl-ferrocenylene)vinylene [poly(tBu2fc-C═C)], negligible Faraday rotation was observed. Hence, Faraday rotation can be maintained when molecular symmetry is broken, however orbital symmetry breaking in optical transitions of interest leads to a significant loss in magneto-optical activity.

Amplified Overhauser DNP with Selective Deuteration: Attenuation of Double-Quantum Cross-Relaxation.

We recently used selective 2H labeling of BDPA to investigate the Overhauser Effect (OE) dynamic nuclear polarization (DNP) mechanism in insulating solids doped with 1,3-bis(diphenylene)-2-phenylallyl (BDPA), and established that the α and γ 1H spins on the fluorene rings are responsible for generating a zero quantum (ZQ) mediated positive bulk polarization. Here, we establish that the phenyl 1H spins relax via double-quantum (DQ) processes and therefore contribute negative enhancements which attenuate the OE-DNP. With measurements at different magnetic field strengths, we show that phenyl-d5-BDPA offers >50% improvement in OE-DNP enhancement compared to h21-BDPA attaining a maximum of ∼90 at 14.1 T and 5 kHz MAS, the highest observed OE-DNP enhancement to date under these conditions. The approach may be utilized to optimize other polarizing agents exhibiting an OE, an important DNP mechanism with a favorable field and spinning frequency dependence.

ABCs of Faraday Rotation in Organic Materials.

Faraday rotation is a magneto-optical effect central to a number of commercial technologies including optical isolation and magneto-optical imaging. Today, the performance needs of these technologies are met by inorganic materials containing paramagnetic heavy elements. However, organic thin films are increasingly being evaluated as replacement materials, promising higher magneto-optical performance and facile fabrication of structures that enable expanded applications. Despite being an object of research for more than 175 years, our understanding of the Faraday effect in solid-state organic materials remains incomplete, hindering our attempts to methodically improve magneto-optical performance. This Perspective aims to place several recent advances in the field of thin-film organic Faraday rotators within the well-established theoretical framework developed by solution-state magnetic circular dichroism spectroscopists: the Faraday A, B, and C terms. Through careful consideration of these quantum mechanical mechanisms in example molecules, an intuitive understanding of the impact of chemical structure in thin-film Faraday rotators can be achieved, including the critical roles of molecular symmetry, rigidity, absorptivity, and magnetism. Future work seeking to maximize the magneto-optical performance of organic thin films may more readily evaluate candidate chromophores based on the Faraday A, B, and C term framework presented herein.

Overhauser Dynamic Nuclear Polarization with Selectively Deuterated BDPA Radicals.

The Overhauser effect (OE), commonly observed in NMR spectra of liquids and conducting solids, was recently discovered in insulating solids doped with the radical 1,3-bisdiphenylene-2-phenylallyl (BDPA). However, the mechanism of polarization transfer in OE-DNP in insulators is yet to be established, but hyperfine coupling of the radical to protons in BDPA has been proposed. In this paper we present a study that addresses the role of hyperfine couplings via the EPR and DNP measurements on some selectively deuterated BDPA radicals synthesized for this purpose. Newly developed synthetic routes enable selective deuteration at orthogonal positions or perdeuteration of the fluorene moieties with 2H incorporation of >93%. The fluorene moieties were subsequently used to synthesize two octadeuterated BDPA radicals, 1,3-[α,γ-d8]-BDPA and 1,3-[ß,δ-d8]-BDPA, and a BDPA radical with perdeuterated fluorene moieties, 1,3-[α,ß,γ,δ-d16]-BDPA. In contrast to the strong positive OE enhancement observed in degassed samples of fully protonated h21-BDPA (ε ∼ +70), perdeuteration of the fluorenes results in a negative enhancement (ε ∼ -13), while selective deuteration of α- and γ-positions (aiso ∼ 5.4 MHz) in BDPA results in a weak negative OE enhancement (ε ∼ -1). Furthermore, deuteration of ß- and δ-positions (aiso ∼ 1.2 MHz) results in a positive OE enhancement (ε ∼ +36), albeit with a reduced magnitude relative to that observed in fully protonated BDPA. Our results clearly show the role of the hyperfine coupled α and γ 1H spins in the BDPA radical in determining the dominance of the zero and double-quantum cross-relaxation pathways and the polarization-transfer mechanism to the bulk matrix.

C-Term Faraday Rotation in Metallocene Containing Thin Films.

The Faraday effect is a magneto-optical (MO) phenomenon that causes the plane of linearly polarized light to rotate when passing through a medium subjected to a parallel magnetic field. Informed by the established quantum mechanical model developed by Buckingham and Stephens, we sought to identify molecules that would exhibit large MO responses. Magnetic circular dichroism studies of ferrocenium in the 1970s revealed its potential as an MO material; however, it has not been evaluated in the context of Faraday rotation and thin-film optical applications. Herein, we report near-infrared (NIR) Faraday rotation in thin films of decamethylferrocenium/poly(methyl methacrylate) composites with maximum Verdet constants of -3.45 × 104 deg T-1 m-1 at 810 nm (absorbance = 0.09) and -1.44 × 104 deg T-1 m-1 at 870 nm (absorbance = 0.01). These polymer-metallocene thin films deliver larger Verdet constants than commercially used NIR inorganic Faraday rotators and are facile and inexpensive to produce. The temperature dependence and distinct lineshape of the MO responses observed in decamethylferrocenium radical cations, decamethylmanganocene, and chromocene are in accordance with the quantum mechanical model. The observation of a strong C-term Faraday rotation in solid-state organometallic materials provides the groundwork for the development of high-performance metallocene-based Faraday rotators.

Large Faraday Rotation in Optical-Quality Phthalocyanine and Porphyrin Thin Films.

The magneto-optical phenomenon known as Faraday rotation involves the rotation of plane-polarized light as it passes through an optical medium in the presence of an external magnetic field oriented parallel to the direction of light propagation. Faraday rotators find applications in optical isolators and magnetic-field imaging technologies. In recent years, organic thin films comprised of polymeric and small-molecule chromophores have demonstrated Verdet constants, which measure the magnitude of rotation at a given magnetic field strength and material thickness, that exceed those found in conventional inorganic crystals. We report herein the thin-film magnetic circular birefringence (MCB) spectra and maximum Verdet constants of several commercially available and newly synthesized phthalocyanine and porphyrin derivatives. Five of these species achieved maximum Verdet constant magnitudes greater than 105 deg T-1 m-1 at wavelengths between 530 and 800 nm. Notably, a newly reported zinc(II) phthalocyanine derivative (ZnPc-OT) reached a Verdet constant of -33 × 104 deg T-1 m-1 at 800 nm, which is among the largest reported for an organic material, especially for an optical-quality thin film. The MCB spectra are consistent with resonance-enhanced Faraday rotation in the region of the Q-band electronic transition common to porphyrin and phthalocyanine derivatives, and the Faraday A-term describes the electronic origin of the magneto-optical activity. Overall, we demonstrate that phthalocyanines and porphyrins are a class of rationally designed magneto-optical materials suitable for applications demanding large Verdet constants and high optical quality.

Copper-Catalyzed Carbenoid Insertion Reactions of α-Diazoesters and α-Diazoketones into Si-H and S-H Bonds.

An efficient copper-catalyzed carbenoid insertion reaction of α-diazo carbonyl compounds into Si-H and S-H bonds was developed. A wide range of α-silylesters and α-thioesters was obtained in high yields (up to 98%) from α-diazoesters using 5 mol% of a simple copper(I) salt as catalyst. Using 0.05 mol% of the same catalyst, α-diazoketones led to α-silylketones in low to good yields (up to 70%).