Organic Synthesis through Radical Innovation:Frustrated Radical Pairs

Frustrated Lewis Pairs(FLPs)represent a unique class of interactions in Lewis acid-base chemistry,driven by spatial hindrance or incongruent orbital energy levels that hinder the formation of effective coordination bonds.FLPs have received significant attention for their application in activating small molecules and facilitating organic synthesis reactions.Recent developments have led to the emergence of Frustrated Radical Pairs(FRPs)as an extension of the radical family.FRPs are formed from FLPs through Single Electron Transfer(SET)and exhibit the ability to activate a variety of chemical bonds.While research on FLPs is well-established,investigations into FRPs in organic reactions remain limited.This review highlights the current state of FRPs in organic synthesis,delves into mechanistic insights,explores their potential,and underscores the challenges in this emerging field.

Avian magnetoreception model realized by coupling a magnetite-based mechanism with a radical-pair-based mechanism

Many animal species have been proven to use the geomagnetic field for their navigation, but the biophysical mechanism of magnetoreception has remained enigmatic. In this paper, we present a special biophysical model that consists of magnetite-based and radical-pair-based mechanisms for avian magnetoreception. The amplitude of the resultant magnetic field around the magnetic particles corresponds to the geomagnetic field direction and affects the yield of singlet/triplet state products in the radical-pair reactions. Therefore, in the proposed model, the singlet/triplet state product yields are related to the geomagnetic field information for orientational detection. The resultant magnetic fields corresponding to two materials with different magnetic properties are analyzed under different geomagnetic field directions. The results show that ferromagnetic particles in organisms can provide more significant changes in singlet state products than superparam- agnetic particles, and the period of variation for the singlet state products with an included angle in the geomagnetic field is approximately 180 when the magnetic particles are ferromagnetic materials, consistent with the experimental results obtained from the avian magnetic compass. Further, the calculated results of the singlet state products in a reception plane show that the proposed model can explain the avian magnetoreception mechanism with an inclination compass.

Stable Radical Ion Pairs Induced by Single Electron Transfer:Frustrated Versus Nonfrustrated

Single electron transition reactions between amines(Lewis base)and B(C_(6)F_(5))_(3)(Lewis acid)in cooperation with benzoquinones gave rise to a frustrated radical pair 3 and a nonfrustrated radical pair 4.Both of them were isolated as stable crystals and studied by single-crystal X-ray diffraction,superconducting quantum interference device measurements,electron paramagnetic resonance,nuclear magnetic resonance,and UV–vis spectroscopy.Antiferromagnetic exchange coupling was observed among both 3 and 4.Radical anion and cation are basically separated in 3,while 4 featured a relatively strong anion-cationπ–πstacking interaction.This work demonstrated that the Lewis acid coupled electron transfer is an efficient way to prepare stable radical ion pairs.

Avian magnetic compass:Its functional properties and physical basis

The avian magnetic compass was analyzed in bird species of three different orders - Passeriforms, Columbiforms and Galliforms - and in three different behavioral contexts, namely migratory orientation, homing and directional conditioning. The respective findings indicate similar functional properties： it is an inclination compass that works only within a functional window around the ambient magnetic field intensity; it tends to be lateralized in favor of the fight eye, and it is wavelength-dependent, requiring light from the short-wavelength range of the spectrum. The underlying physical mechanisms have been identified as radical pair processes, spin-chemical reactions in specialized photopigments. The iron-based receptors in the upper beak do not seem to be involved. The existence of the same type of magnetic compass in only very distantly related bird species suggests that it may have been present already in the common ancestors of all modem birds, where it evolved as an all-purpose compass mechanism for orientation within the home range [Current Zoology 56 （3）： 265-276, 2010].