Singlet fission (SF), a process by which two excited states are formed in a chromophoric system following the absorption of a single photon, has the potential to increase the theoretical efficiency of solar energy conversion devices beyond the single-junction Shockley-Quiesser limit. Although SF is observed with high yield in the solid state of certain molecules, linearly linked dimers based on these same constituents exhibit small yields in part due to small interchromophore electronic coupling. Previous work from our group demonstrated enhancement of SF yield in polycrystalline tetracene (Tc) via excitation of intermolecular motions, which increased direct overlap of monomer π-systems. In this current work, a series of norbornyl-bridged bistetracene (BT) dimers are investigated using DFT and the ability to control SF thermodynamics along with important interchromophore electronic coupling parameters via bridging geometry is shown. Although the electronic coupling of a series of C2v-symmetric dimers (BT1-BT3) that differ in norbornyl bridge length is larger than in previously studied Tc dimers, a key nonhorizontal electron-transfer (ET) matrix element used in determining the SF rate is zero due to symmetry. In these systems, SF may be expected but electronic excitation will require coupling to vibrational modes that break symmetry. Singly bridged dimer isomers BT1-trans and BT1-cis, which break the C2v symmetry of BT1 by exploiting attachment of the norbornyl bridge at the 1,2 instead of the 2,3 Tc positions, are expected to be significantly more favorable for SF due to an exoergic driving force, increased electronic coupling, a lower charge-transfer-state energy (particularly in the case of BT1-cis), and nonhorizontal ET matrix elements that are nonzero.

While singlet fission (SF) has developed in recent years within material settings, much less is known about its control in covalent dimers. Such platforms are of fundamental importance and may also find practical use in next-generation dye-sensitized solar cell applications or for seeding SF at interfaces following exciton transport. Here, facile theoretical tools based on Boys localization methods are used to predict diabatic coupling for SF via determination of one-electron orbital coupling matrix elements. The results expose important design rules that are rooted in point group symmetry. For Cs-symmetric dimers, pathways for SF that are mediated by virtual charge transfer excited states destructively interfere with negative impact on the magnitude of diabatic coupling for SF. When dimers have C2 symmetry, constructive interference is enabled for certain readily achievable interchromophore orientations. Three sets of dimers exploiting these ideas are explored: a bis-tetracene pair and two sets of aza-substituted tetracene dimers. Remarkable control is shown. In one aza-substituted set, symmetry has no impact on SF reaction thermodynamics but leads to a 16-fold manipulation in SF diabatic coupling. This translates to a difference of nearly 300 in kSF with the faster of the two dimers (C2) being predicted to undergo the process on a nearly ultrafast 1.5 ps time scale.

We report the first synthesis of norbornyl-bridged acene dimers (2 and 3) with well-defined and controlled spatial relationships between the acene chromophore subunits. We employ a modular 2-D strategy wherein the central module, common to all our compounds, is a norbornyl moiety. The acenes are attached to this module using the Diels-Alder reaction, which also forms one of the acene rings. Manipulation of the Diels-Alder adducts provides the desired geometrically defined bis-acenes. The modular nature of this synthesis affords flexibility and allows for the preparation of a variety of acene dimers, including functionalized tetracene dimers.

Diruthenium azido complexes Ru(2)(DPhF)(4)N(3) (1a, DPhF = N,N'-diphenylformamidinate) and Ru(2)(D(3,5-Cl(2))PhF)(4)N(3) (1b, D(3,5-Cl(2))PhF = N,N'-bis(3,5-dichlorophenyl)formamidinate) have been investigated by thermolytic and photolytic experiments to investigate the chemical reactivity of the corresponding diruthenium nitride species. Thermolysis of 1b at ~100 °C leads to the expulsion of N(2) and isolation of Ru(2)(D(3,5-Cl(2))PhF)(3)NH(C(13)H(6)N(2)Cl(4)) (3b), in which a nitrogen atom has been inserted into one of the proximal aryl C-H bonds of a D(3,5-Cl(2))PhF ligand. A similar C-H insertion product is obtained upon thawing a frozen CH(2)Cl(2) solution of the nitride complex Ru(2)(DPhF)(4)N (2a), formed via photolysis at -196 °C of 1a to yield Ru(2)(DPhF)(3)NH(C(13)H(10)N(2)) (3a). Evidence is provided here that both reactions proceed via direct intramolecular attack of an electrophilic terminal nitrido nitrogen atom on a proximal aryl ring. Thermodynamic and kinetic data for this reaction are obtained from differential scanning calorimetric measurements and thermal gravimetric analysis of the thermolysis of Ru(2)(D(3,5-Cl(2))PhF)(4)N(3), and by Arrhenius/Eyring analysis of the conversion of Ru(2)(DPhF)(4)N to its C-H insertion product, respectively. These data are used to develop a detailed, experimentally validated DFT reaction pathway for N(2) extrusion and C-H functionalization from Ru(2)(D(3,5-Cl(2))PhF)(4)N(3). The diruthenium nitrido complex is an intermediate in the calculated reaction pathway, and the C-H functionalization event shares a close resemblance to a classical electrophilic aromatic substitution mechanism.

The reaction of Ru(2)(OAc)(4)Cl with N,N',N''-triphenylguanidine (HTPG) produces one of two different compounds depending on the reaction conditions. In acetone in the presence of triethyl amine, the reaction produces tri-substituted Ru(2)(TPG)(3)(OAc)Cl, and in refluxing xylene, the tetra-substituted Ru(2)(TPG)(4)Cl is produced. Both of these new complexes can be cleanly converted into their corresponding azido analogues by reaction with sodium azide in methanol. The X-ray crystal structures of Ru(2)(TPG)(3)(OAc)Cl, Ru(2)(TPG)(3)(OAc)N(3), and Ru(2)(TPG)(4)Cl are presented, along with magnetic, electrochemical, and spectral measurements for each compound. Studies in solution show that, in contrast to Ru(2)(TPG)(3)(OAc)Cl, Ru(2)(TPG)(4)Cl is sterically hindered at the axial positions, and readily dissociates a chloride ion at high ionic strength. Equilibrium constants for chloride association and dissociation have been estimated. Mass spectrometric data suggest that the two azido complexes are precursors to new diruthenium nitrido species.