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π-Conjugated molecules are viewed as fundamental components in forthcoming molecular nanoelectronics in which semiconducting functional units are linked to each other via metallic molecular wires. However, it is still challenging to construct such block cooligomers on the surface. Here, we present a synthesis of [18]-polyene-linked Zn-porphyrin cooligomers via a two-step reaction of the alkyl groups on Cu(111) and Cu(110). Nonyl groups (-C 9 H 19 ) substituted at the 5,15- meso positions of Zn-porphyrin were first transformed to alkenyl groups (-C 9 H 10 ) by dehydrogenation. Subsequently, homocoupling of the terminal -CH 2 groups resulted in the formation of extended [18]-polyene-linked porphyrin cooligomers. The structures of the products at each reaction step were investigated by bond-resolved scanning tunneling microscopy at low temperatures. A combination of angle-resolved photoemission spectroscopy and density functional theory calculations revealed the metallic property of the all trans [18]-polyene linker on Cu(110). This finding may provide an approach to fabricate complex nanocarbon structures on the surface.

Tracking the behavior of mechanochromic molecules provides valuable insights into force transmission and associated microstructural changes in soft materials under load. Herein, we report a dual ratiometric fluorescence (FL) analysis for monitoring both mechanical polymer chain stretching and strain-induced crystallization (SIC) of polymers. SIC has recently attracted renewed attention as an effective mechanism for improving the mechanical properties of polymers. A polyurethane (PU) film incorporating a trace of a dual-emissive flapping force probe (N-FLAP, 0.008 wt %) exhibited a blue-to-green FL spectral change in a low-stress region (<20 MPa), resulting from conformational planarization of the probe in mechanically stretched polymer chains. More importantly, at higher probe concentrations (∼0.65 wt %), the PU film showed a second spectral change from green to yellow during the SIC growth (20-65 MPa) due to self-absorption of scattered FL in a short wavelength region. The reversibility of these spectral changes was demonstrated by load-unload cycles. With these results in hand, the degrees of the polymer chain stretching and the SIC were quantitatively mapped and monitored by dual ratiometric imaging based on different FL ratios ( I 525 / I 470 and I 525 / I 600 ). Simultaneous analysis of these two mappings revealed a spatiotemporal gap in the distribution of the polymer chain stretching and the SIC. The combinational use of the dual-emissive force probe and the ratiometric FL imaging is a universal approach for the development of soft matter physics.

Polymer gels have recently attracted attention for their application in flexible devices, where mechanically robust gels are required. While there are many strategies to produce tough gels by suppressing nanoscale stress concentration on specific polymer chains, it is still challenging to directly verify the toughening mechanism at the molecular level. To solve this problem, the use of the flapping molecular force probe (FLAP) is promising because it can evaluate the nanoscale forces transmitted in the polymer chain network by ratiometric analysis of a stress-dependent dual fluorescence. A flexible conformational change of FLAP enables real-time and reversible responses to the nanoscale forces at the low force threshold, which is suitable for quantifying the percentage of the stressed polymer chains before structural damage. However, the previously reported FLAP only showed a negligible response in solvated environments because undesirable spontaneous planarization occurs in the excited state, even without mechanical force. Here, we have developed a new ratiometric force probe that functions in common organogels. Replacement of the anthraceneimide units in the flapping wings with pyreneimide units largely suppresses the excited-state planarization, leading to the force probe function under wet conditions. The FLAP-doped polyurethane organogel reversibly shows a dual-fluorescence response under sub-MPa compression. Moreover, the structurally modified FLAP is also advantageous in the wide dynamic range of its fluorescence response in solvent-free elastomers, enabling clearer ratiometric fluorescence imaging of the molecular-level stress concentration during crack growth in a stretched polyurethane film.

Single-molecule spectroscopy (SMS) of a dual fluorescent flapping molecular probe (N-FLAP) enabled real-time nanoscale monitoring of local free volume dynamics in polystyrenes. The SMS study was realized by structural improvement of a previously reported flapping molecule by nitrogen substitution, leading to increased brightness (22 times) of the probe. In a polystyrene thin film at the temperature of 5 K above the glass transition, the spectra of a single N-FLAP molecule undergo frequent jumps between short- and long-wavelength forms, the latter one indicating planarization of the molecule in the excited state. The observed spectral jumps were statistically analyzed to reveal the dynamics of the molecular environment. The analysis together with MD and QM/MM calculations show that the excited-state planarization of the flapping probe occurs only when sufficiently large polymer free volume of more than, at least, 280 Å 3 is available close to the molecule, and that such free volume lasts for an average of 1.2 s.

Mechanical control of the molecular energy landscape is an important issue in modern materials science. Mechanophores play a unique role in that the mechanical responses are induced against the activation barrier for intramolecular transformation with the aid of external forces. Here we report an unprecedented activation process of a flexible flapping mechanophore. Namely, thermal void collapse in a crystalline phase triggers mechanophore compression in a definite proportion. Unfavored conformational planarization of the flapping mechanophore is compulsorily induced by packing force, leading to a total energy gain in crystal packing. Fluorescence chromism indicates extended π conjugation resulting from the mechanophore compression, giving rise to an energy transfer from the unpressed to compressed conformers.