Supramolecular p−n-Heterojunctions by Co-Self-Organization of Oligo(p-phenylene Vinylene) and Perylene Bisimide Dyes

Abstract

Comparative studies on hydrogen-bonded versus covalently linked donor-acceptor-donor dye arrays obtained from oligo(p-phenylene vinylene)s (OPVs) as donor and bay-substituted perylene bisimides (PERYs) as acceptor dyes are presented. Both systems form well-ordered J-type aggregates in methylcyclohexane, but only hydrogen-bonded arrays afford hierarchically assembled chiral OPV-PERY dye superstructures consisting of left-handed helical pi-pi co-aggregates (CD spectroscopy) of the two dyes that further assemble into right-handed nanometer-scale supercoils in the solid state (AFM study). In the case of hydrogen-bonded arrays, the stability of the aggregates in solution increases with increasing conjugation length of the OPV unit. The well-defined co-aggregated dyes presented here exhibit photoinduced electron transfer on subpicosecond time scale, and thus, these supramolecular entities might serve as valuable nanoscopic functional units.

Ultrafast excited-state dynamics of strongly coupled porphyrin/core-substituted-naphthalenediimide dyads

“…The synthesis of FbTPPNDI (1) and ZnTPPNDI (2) is described in detail in the ESI.w In brief, FbTPPNDI (1) and ZnTPPNDI (2) were synthesized by the condensation of the ortho-diamine functionalized NDI with tetraphenylporphyrin-2,3-dione in a high yield (Scheme 2). Synthesis of diamino-annulated NDIs 3 began by performing condensation of 2,3,6,7-tetrabromonaphthalene diimide 5 25 and 1,2-diamino-4,5-bis(p-toluenesulfonamido) benzene precursor 6 26-28 under argon atmosphere in dry DMF at 135 1C, giving green crystalline solid of 7 (HBNDI) in 87% yields.…”

“…30,31 FbTPPNDI was achieved by the condensation of the ortho-diamine NDI 3 with 4 in DCM/pyridine at 45 1C yielding 1 in 89% yield as a purple solid. Finally ZnTPPNDI 2 was achieved in 96% yield by metallation of 1 with using Zn(OAc) 2 in CHCl 3 /MeOH at room temperature.…”

“…[1][2][3][4][5][6][7][8] The marriage of chemically different chromophoric pieces into a single molecular system results into a chemical entity either combining the properties of each unit or exhibiting novel features. The key parameter for this outcome is the coupling between the chromophores.…”

π-Conjugated polymer-layered structures: synthesis and self-assembly

“…[3][4][5][6][7][8][9][10][11] Because π-conjugated compounds tend to aggregate by π-π stacking, the introduction of non-covalent interactions at appropriate positions increases their association constants and facilitates the formation of higher-ordered structures. 12,13 For example, supramolecular gels can be formed through intermolecular interactions such as hydrogen bonds, 14,15 and multiple long alkyl chains facilitate columnar stacking along the π-stacking direction of supramolecular assemblies [16][17][18][19] (Figure 1a).…”

Topologically Matching Supramolecular n/p‐Heterojunction Architectures

“…However, reliable bottom-up routes toward OMARG-SHJs do not exist to date, despite efforts by many groups. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] We have considered the zipper assembly of naphthalenediimide (NDI) p stacks along poligophenyl (POP) scaffolds to construct the surface architectures needed to tackle this challenge. [20][21][22] Herein, we introduce oligophenylethynyl (OPE) scaffolds to explore the importance of topological matching for zipper architectures and to determine the compatibility of zipper assembly with the creation of OMARG-SHJs.…”