Ultrafast Solvation Dynamics and Vibrational Coherences of Halogenated Boron-Dipyrromethene Derivatives Revealed through Two-Dimensional Electronic Spectroscopy.

Boron-dipyrromethene (BODIPY) chromophores have a wide range of applications, spanning areas from biological imaging to solar energy conversion. Understanding the ultrafast dynamics of electronically excited BODIPY chromophores could lead to further advances in these areas. In this work, we characterize and compare the ultrafast dynamics of halogenated BODIPY chromophores through applying two-dimensional electronic spectroscopy (2DES). Through our studies, we demonstrate a new data analysis procedure for extracting the dynamic Stokes shift from 2DES spectra revealing an ultrafast solvent relaxation. In addition, we extract the frequency of the vibrational modes that are strongly coupled to the electronic excitation, and compare the results of structurally different BODIPY chromophores. We interpret our results with the aid of DFT calculations, finding that structural modifications lead to changes in the frequency, identity, and magnitude of Franck-Condon active vibrational modes. We attribute these changes to differences in the electron density of the electronic states of the structurally different BODIPY chromophores.

Aza-Glycine Induces Collagen Hyperstability.

Hydrogen bonding is fundamental to life on our planet, and nature utilizes H-bonding in nearly all biomolecular interactions. Often, H-bonding is already maximized in natural biopolymer systems such as nucleic acids, where Watson-Crick H-bonds are fully paired in double-helical structures. Synthetic chemistry allows molecular editing of biopolymers beyond nature's capability. Here we demonstrate that substitution of glycine (Gly) with aza-glycine in collagen may increase the number of interfacial cross-strand H-bonds, leading to hyperstability in the triple-helical form. Gly is the only amino acid that has remained intolerant to substitution in collagen. Our results highlight the vital importance of maximizing H-bonding in higher order biopolymer systems using minimally perturbing alternatives to nature's building blocks.

A Single Stereodynamic Center Modulates the Rate of Self-Assembly in a Biomolecular System.

Chirality is a property of asymmetry important to both physical and abstract systems. Understanding how molecular systems respond to perturbations in their chiral building blocks can provide insight into diverse areas such as biomolecular self-assembly, protein folding, drug design, materials, and catalysis. Despite the fundamental importance of stereochemical preorganization in nature and designed materials, the ramifications of replacing chiral centers with stereodynamic atomic mimics in the context of biomolecular systems is unknown. Herein, we demonstrate that replacement of a single amino acid stereocenter with a stereodynamic nitrogen atom has profound consequences on the self-assembly of a biomolecular system. Our results provide insight into how the fundamental biopolymers of life would behave if their chiral centers were not configurationally stable, highlighting the vital importance of stereochemistry as a pre-organizing element in biomolecular folding and assembly events.

Halogen Bonding Facilitates Intersystem Crossing in Iodo-BODIPY Chromophores.

BODIPY chromophores can serve as organic-based triplet photosensitizers for a wide range of applications. To perform this function, the formation of the triplet state is critical, and a better understanding of how to modulate the formation of the triplet state could lead to further advances in BODIPY-based sensitizers for solar energy conversion and photodynamic therapy. In this work we investigate the ability of halogen bonding, a noncovalent solvent interaction, to facilitate intersystem crossing in a diiodo-BODIPY. Ultrafast transient absorption spectroscopy is applied to diiodo-BODIPY in the presence of pyridine-based halogen bonding solvent molecules to determine the rate constants for intersystem crossing. We find that halogen bonding facilitates the formation of the triplet state by increasing the intersystem crossing rate constant of diiodo-BODIPY. The results are interpreted in terms of the Marcus expression for intersystem crossing. Quantum chemical calculations show that halogen bonding acts to alter both the spin-orbit coupling terms and the relative energetics of the singlet and triplet states.

Highly efficient diastereoselective reduction of alpha-fluoroimines.

A highly selective reduction of alpha-fluoroimines to the corresponding beta-fluoroamines has been developed utilizing trichlorosilane as the reductant. The key aspect of this reaction is the ability of fluorine and nitrogen to activate organosilanes leading to high diastereoselectivity (>100:1) in the product distribution. This new method provides a new avenue for the diastereoselective synthesis of beta-fluorinated amines in good yields and selectivity.