Molecular aggregates with long-range excitonic couplings have drastically different photophysical properties compared to their monomer counterparts. From Kasha's model for one-dimensional systems, positive or negative lead blue red-shifted optical spectra respect the monomers, labeled H-and J-aggregates, respectively. The overall in higher dimensional systems are much more complicated and cannot be simply classified from spectral shifts alone. Here, we provide a unified classification...

Excitonic chromophore aggregates have wide-ranging applicability in fields such as imaging and energy harvesting; however their rational design requires adapting principles of self-assembly to the requirements excited state coupling.

Optical imaging in the shortwave infrared region (SWIR, 1000–2000 nm) provides high-resolution images complex systems. Here we explore substituent placement on dimethylamino flavylium polymethine dyes, a class of SWIR fluorophores. We find that position significantly affects λmax and fluorescence quantum yield. Quantum-mechanical calculations suggest steric clashes control extent π-conjugation. These insights provide design principles for development fluorophores enhanced imaging.

Incorporation of silicon into heterocycles for polymethine dyes can impart red-shifts up to 100 nm, while also enhancing photostability 10-fold, resulting in photostable fluorophores with emission above 900 nm.

Polymethine fluorophores have facilitated the advance of biological and material sciences, due to their advantageous photophysical properties. However, need maintain a monomeric state can severely limit utility processability dyes. High concentrations fluorophore lead aggregation negate beneficial properties monomers. Another concern is "crossing cyanine limit" in which delocalization within polymethine scaffold broken, producing presence an asymmetric diminishing its behavior. Herein, we...

Molecular design of two-dimensional (2D) and tubular excitonic aggregates would enable access to extraordinary unusual photophysical properties via control over supramolecular structure. Here, we synthesize four heptamethine cyanines that a rational investigation the role steric bulk on aggregate self-assembly, morphology photophysics. Despite near identical monomer photophysics, minute changes structure solvation lead extreme differences in resultant J-aggregate Additional not only...

Molecular aggregates with long-range excitonic couplings have drastically different photophysical properties compared to their monomer counterparts. From Kasha’s model for 1-dimensional systems, positive or negative lead blue red shifted optical spectra respect the monomers, labelled H-and J-aggregates respectively. The overall in higher dimensional systems are much more complicated and cannot be simply classified from spectral shifts alone. Here, we provide a unified classification extended...

Developing improved organic infrared emitters has wide-ranging applicability in fields such as bioimaging or energy harvesting. We synthesize redshifted analogues of C8S3, a well-known cyanine dye that self assembles into tubular aggregates which have attracted widespread attention artificial photosynthetic complexes. Despite the elongated structure, new pentamethine dyes retain their self-assembly and emit at near-infrared wavelengths. Cryo-electron microscopy detailed photophysical...

Developing improved organic infrared emitters has wide-ranging applicability in fields such as bioimaging or energy harvesting. We synthesize redshifted analogues of C8S3, a well-known cyanine dye that self assembles into tubular aggregates which have attracted widespread attention artificial photosynthetic complexes. Despite the elongated structure, new pentamethine dyes retain their self-assembly and emit at near-infrared wavelengths. Cryo-electron microscopy detailed photophysical...

Excitonic chromophore aggregates have wide-ranging applicability in fields such as imaging and energy harvesting, however their rational design requires adapting principles of self-assembly to the requirements excited state coupling. Using well-studied amphiphilic cyanine dye C8S3 a template—known assemble into tubular excitonic aggregates—we synthesize several redshifted variants study photophysics. The new pentamethine dyes retain demonstrate nearly identical bathochromic shifts lineshapes...

Methods to red-shift fluorophores have garnered considerable interest due the broad utility of low energy light. The incorporation silicon into xanthene scaffolds has resulted in an array visible and near-infrared fluorophores. Here, we extend this approach polymethine dyes, another popular fluorophore class. We found that when oxygen was replaced with SiMe 2 , bathochromic shifts up 121 nm emission above 900 were achieved.

<p>Methods to red-shift fluorophores have garnered considerable interest due the broad utility of low energy light. The incorporation silicon into xanthene and coumarin scaffolds has resulted in an array visible near-infrared fluorophores. Here, we extend this approach polymethine dyes, another popular fluorophore class, performing experimental computational analyses. We found that when oxygen was replaced with SiMe<sub>2,</sub> bathochromic shifts up 121 nm emission above...

Methods to red-shift fluorophores have garnered considerable interest due the broad utility of low energy light. The incorporation silicon into xanthene and coumarin scaffolds has resulted in an array visible near-infrared fluorophores. Here, we extend this approach polymethine dyes, another popular fluorophore class, performing experimental computational analyses. We found that when oxygen was replaced with SiMe 2, bathochromic shifts up 121 nm emission above 900 were achieved.

Molecular aggregates with long-range excitonic couplings have drastically different photophysical properties compared to their monomer counterparts. From Kasha’s model for 1-dimensional systems, positive or negative lead blue red shifted optical spectra respect the monomers, labelled H-and J-aggregates respectively. The overall in higher dimensional systems are much more complicated and cannot be simply classified from spectral shifts alone. Here, we provide a unified classification extended...

Excitonic chromophore aggregates have wide-ranging applicability in fields such as imaging and energy harvesting, however their rational design requires adapting principles of self-assembly to the requirements excited state coupling. Using well-studied amphiphilic cyanine dye C8S3 a template—known assemble into tubular excitonic aggregates—we synthesize several redshifted variants study photophysics. The new pentamethine dyes retain demonstrate nearly identical bathochromic shifts lineshapes...

Developing improved organic infrared emitters has wide-ranging applicability in fields such as bioimaging or energy harvesting. We synthesize redshifted analogues of C8S3, a well-known cyanine dye that self assembles into tubular aggregates which have attracted widespread attention artificial photosynthetic complexes. Despite the elongated structure, new pentamethine dyes retain their self-assembly and emit at near-infrared wavelengths. Cryo-electron microscopy detailed photophysical...

Developing improved organic infrared emitters has wide-ranging applicability in fields such as bioimaging or energy harvesting. We synthesize redshifted analogues of C8S3, a well-known cyanine dye that self assembles into tubular aggregates which have attracted widespread attention artificial photosynthetic complexes. Despite the elongated structure, new pentamethine dyes retain their self-assembly and emit at near-infrared wavelengths. Cryo-electron microscopy detailed photophysical...

Molecular aggregates with long-range excitonic couplings have drastically different photophysical properties compared to their monomer counterparts. From Kasha’s model for 1-dimensional systems, positive or negative lead blue red shifted optical spectra respect the monomers, labelled H-and J-aggregates respectively. The overall in higher dimensional systems are much more complicated and cannot be simply classified from spectral shifts alone. Here, we provide a unified classification extended...

Molecular aggregates with long-range excitonic couplings have drastically different photophysical properties compared to their monomer counterparts. From Kasha’s model for 1-dimensional systems, positive or negative lead blue red shifted optical spectra respect the monomers, labelled H-and J-aggregates respectively. The overall in higher dimensional systems are much more complicated and cannot be simply classified from spectral shifts alone. Here, we provide a unified classification extended...

Molecular aggregates with long-range excitonic couplings have drastically different photophysical properties compared to their monomer counterparts. From Kasha’s model for 1-dimensional systems, positive or negative lead blue red shifted optical spectra respect the monomers, labelled H-and J-aggregates respectively. The overall in higher dimensional systems are much more complicated and cannot be simply classified from spectral shifts alone. Here, we provide a unified classification extended...