Self-Organizing Surface-Initiated Polymerization: Facile Access to Complex Functional Systems

Sakai, Naomi; Lista, Marco; Kel, Oksana; Sakurai, Shinichiro; Emery, Daniel; Mareda, Jiri; Vauthey, Eric; Matile, Stefan

doi:10.1021/ja203792n

Cited by 136 publications

(152 citation statements)

References 39 publications

Supporting

Mentioning

149

Contrasting

Unclassified

Order By: Relevance

“…For SOSIP [18–19], the concentration of propagators had to be optimized to a critical SOSIP concentration, c SOSIP . Below c SOSIP , ring-opening disulfide-exchange polymerization [27] does not occur, whereas above c SOSIP , the polymerization occurs everywhere, not only on the surface but also in solution.…”

Section: Resultsmentioning

confidence: 99%

Multistep organic synthesis of modular photosystems

Sakai¹,

Matile²

2012

Beilstein J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

SummaryQuite extensive synthetic achievements vanish in the online supporting information of publications on functional systems. Underappreciated, their value is recognized by experts only. As an example, we here focus in on the recent synthesis of multicomponent photosystems with antiparallel charge-transfer cascades in co-axial hole- and electron-transporting channels. The synthetic steps are described one-by-one, starting with commercial starting materials and moving on to key intermediates, such as asparagusic acid, an intriguing natural product, as well as diphosphonate “feet”, and panchromatic naphthalenediimides (NDIs), to finally reach the target molecules. These products are initiators and propagators for self-organizing surface-initiated polymerization (SOSIP), a new method introduced to secure facile access to complex architectures. Chemoorthogonal to the ring-opening disulfide exchange used for SOSIP, hydrazone exchange is then introduced to achieve stack exchange, which is a “switching” technology invented to drill giant holes into SOSIP architectures and fill them with functional π-stacks of free choice.

show abstract

Section: Resultsmentioning

confidence: 99%

Multistep organic synthesis of modular photosystems

Sakai¹,

Matile²

2012

Beilstein J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…[1][2][3][4][5][6][7][8][9][10][11] A large number of chromophores is advantageous for increasing the absorption cross-section, but too high a density augments the mutual interactions and considerably changes the photophysical properties. In natural systems, this problem is prevented by the proteinic scaffold, which holds the pigments at distances and/or orientations that keep coupling small but sufficient to enable excitation energy and/or charge transfer.…”

Section: Introductionmentioning

confidence: 99%

“…10,27 Both D and A are naphthalenediimide (NDI) chromophores: A is substituted on the N atoms only, is colorless with absorption below 400 nm and will be called further on p(ale)NDI; D is additionally substituted at the naphthalene core with an amino group and a Br atom, is red coloured, 28 and will abbreviated r(ed)NDI. The SOSIP systems produce photocurrent when used a working electrode in the presence of a mobile electron donor and a counter electrode.…”

Section: Introductionmentioning

confidence: 99%

Comparison of Charge-Transfer Dynamics of Naphthalenediimide Triads in Solution and π-Stack Architectures on Solid Surfaces

et al. 2015

Self Cite

View full text Add to dashboard Cite

The femto- to microsecond excited-state dynamics of an electron donor–acceptor–donor triad, consisting of two red core-substituted naphthalenediimides (rNDI) and one colorless naphthalenediimide (pNDI), in solution has been compared to that of a supramolecular surface architecture, constituted of coaxial stacks of rNDI and pNDI and prepared by self-organizing surface initiated polymerization (SOSIP). In the triad, charge separation between an excited rNDI and pNDI takes place in highly polar solvents only and for a subensemble of molecules, around 30%, with a folded conformation. Other processes, such as singlet and triplet excitation energy transfer from pNDI to rNDI and intersystem crossing, are also operative. Additionally, bimolecular symmetry-breaking charge separation upon triplet–triplet annihilation is observed on the microsecond time scale in polar solvent. In the surface architecture, excitation of an rNDI is followed by an ultrafast symmetry breaking-charge separation resulting in a charge-transfer exciton, which either recombines or dissociates into a charge-separated state with the electron and the hole in different stacks. The same charge-separated state can also be populated upon excitation of pNDI, either via a charge-transfer pNDI exciton or after excitation energy transfer to rNDI. Charge recombination in the SOSIP film takes place on a wide range of time scales, ranging from a few picoseconds to several hundreds of microseconds

show abstract

“…[2] More recently,the Matile group developed sophisticated synthetic methods,referred to as self-organizing surface-initiated polymerization, [3] that rely on the ring opening of cyclic disulfide monomers to produce synthetic photosystems.…”

mentioning

confidence: 99%

Kinetically Controlled Sequential Growth of Surface‐Grafted Chiral Supramolecular Copolymers

et al. 2016

View full text Add to dashboard Cite

We report a facile strategy to grow supramolecular copolymers on Au surfaces by successively exposing a surface-anchored monomer to solutions of oppositely charged peptide comonomers. Charge regulation on the active chain end of the polymer sufficiently slows down the kinetics of the self-assembly process to produce kinetically trapped copolymers at near-neutral pH. We thereby achieve architectural control at three levels: The β-sheet sequences direct the polymerization away from the surface, the height of the supramolecular copolymer brushes is well-controlled by the stepwise nature of the alternating copolymer growth, and 2D spatial resolution is realized by using micropatterned initiating monomers. The programmable nature of the resulting architectures renders this concept attractive for the development of customized biomaterials or chiral interfaces for optoelectronics and sensor applications.

show abstract

Self-Organizing Surface-Initiated Polymerization: Facile Access to Complex Functional Systems

Cited by 136 publications

References 39 publications

Multistep organic synthesis of modular photosystems

Multistep organic synthesis of modular photosystems

Comparison of Charge-Transfer Dynamics of Naphthalenediimide Triads in Solution and π-Stack Architectures on Solid Surfaces

Kinetically Controlled Sequential Growth of Surface‐Grafted Chiral Supramolecular Copolymers

Contact Info

Product

Resources

About