* solvent and impurities upplementary Figure 1. 1 H MR spectrum of 3b in CDCl 3 (1.3 mm).
upplementary Figure 2. 13 C MR spectrum of 3b in CDCl 3 (1.3 mm).
upplementary Figure 3. 1 H MR spectrum of 4a in CDCl 3.
upplementary Figure 4. 13 C MR spectrum of 4a in CDCl 3.
upplementary Figure 5. 1 H MR spectrum of 5a in CDCl 3.
* * upplementary Figure 6. 13 C MR spectrum of 5a in CDCl 3.
* * * upplementary Figure 7. 1 H MR spectrum of 4b in CDCl 3.
* * upplementary Figure 8. 13 C MR spectrum of 4b in CDCl 3.
upplementary Figure 9. 1 H MR spectrum of 5b in CDCl 3.
upplementary Figure 10. 13 C MR spectrum of 5b in CDCl 3.
328 K 323 K 313 K 303 K 293 K 283 K 273 K 263 K 253 K 243 K 233 K 223 K 213 K upplementary Figure 11. Temperature dependence of 1 H MR chemical shifts of 5b (CDCl 3, 213 328 K).
δ( 1 H) (ppm) δ (5b-stacked) = 3.815 ppm δ (5b-nonstacked) = 1.923 ppm 1 / T (1 / K) δ( 1 H) (ppm) δ (5b-stacked) = 5.066 ppm δ (5b-nonstacked) = 2.710 ppm 1 / T (1 / K) i 5b-nonstacked 5b-stacked upplementary Figure 12. 1 H MR chemical shifts of 5b in CDCl 3 plotted as a function of temperature. Filled circles represent experimental points. olid curves correspond to chemical shift calculated from the van t Hoff equation.
upplementary Figure 13. X-ray crystal structure of 3b. (a) Top view and (b) side view. The thermal ellipsoids are scaled at 50% probability level. The phenyl groups are omitted for clarity. upplementary Figure 14. X-ray crystal structure of 5b. (a) Top view and (b) side view. The thermal ellipsoids are scaled at 50% probability level.
1.375 1.366 1.378 1.475 1.491 1.383 1.383 1.482 1.467 1.413 1.382 1.422 1.402 1.434 1.386 1.439 1.363 1.423 1.352 1.332 1.378 1.446 1.447 1.363 1.403 1.403 1.363 1.447 1.446 1.332 1.352 1.423 1.382 1.491 1.413 1.434 1.402 3a HOMA = 0.45 1.437 1.350 1.352 1.372 1.435 1.441 1.360 1.417 1.419 1.366 1.441 1.460 1.350 1.350 1.429 1.388 1.486 5b HOMA = 0.54 1.406 1.421 1.394 1.422 1.387 1.428 1.378 1.424 1.438 1.350 1.350 1.366 1.451 1.441 1.364 1.422 1.422 1.441 1.364 1.451 1.350 1.350 1.438 1.378 1.475 1.422 1.428 1.387 1.431 3b (center) 3b (outer) HOMA = 0.56 HOMA = 0.58 1.393 1.430 1.375 1.436 1.355 1.344 1.377 1.440 1.434 1.369 1.419 1.420 1.385 1.428 1.453 1.343 1.350 1.427 5b HOMA = 0.56 1.403 1.474 1.417 1.418 1.390 1.428 1.386 1.369 1.434 1.422 1.472 1.396 1.427 1.379 1.345 1.341 1.349 1.347 1.371 1.445 1.428 1.438 1.366 1.418 1.384 1.4421.382 M 1.419 1.382 1.436 1.368 1.433 1.441 1.344 1.353 1.442 1.384 1.428 1.375 1.478 1.421 1.341 1.431 1.383 Tetramesitylporphyrin (II) HOMA = 0.77 1.434 1.369 1.386 1.428 1.345 upplementary Figure 15. HOMA values of 3a, 3b, 5b and tetramesitylporphyrin (II) in their X-ray structures. The bonds used for HOMA calculations are indicated in bold lines.
upplementary Figure 16. Temperature dependent absorption spectra of 5b at 297 and 77 K in 2-methyl- tetrahydrofuran.
upplementary Figure 17. Two photon absorption cross-section values of (a) 3a, (b) 5a and (c) 5b measured at 1600, 1700, 1800, and 1900 nm in toluene.
upplementary Figure 18. ACID plots of 3a (left) and 5b (right). Calculations were conducted on the X-ray structures at the CGT-B3LYP/6-31G(d) level.
upplementary Figure 19. IC plots of 3a and 5b at a 0.5 Å grid on the perpendicular plane to the π-systems. Calculations were conducted on the X-ray structures at the GIAO-B3LYP/6-31G(d) level.
MO diagram Calculated at B3LYP/6-31G(d) i ev i 1.5 3b 5b 2.5 3.5 1.45 ev 1.47 ev 4.5 5.5 upplementary Figure 20. Frontier molecular orbitals of 3b and 5b at the B3LYP/6-31G(d).
upplementary Figure 21. Wiberg bond order plots for norcorrole dimer and porphyrin dimer at different stacking distances.
upplementary Table 1. ummary of Crystallographic data for 3b and 5b. 3b 5b empirical formula 3(C 30 H 18 4 ) C 64 H 40 8 2 2, 2(CHCl 3 ) formula weight habit T, K crystal system space group a, Å b, Å c, Å α, deg β, deg γ, deg V, Å 3 Z Dc, g/cm 3 F(000) crystal size, mm 3 2θ max, 1479.58 prism 153(2) Monoclinic P2 1 /c 13.6420(11) 11.1624(9) 21.3653(16) 90.00 95.271(2) 90.00 3239.7(4) 2 1.517 1524 0.40 0.40 0.20 56.62 1341.28 block 93 Monoclinic C2/c 24.7680(2) 13.84760(10) 33.0065(3) 90.0000 99.5763(4) 90.0000 11162.73(16) 8 1.596 2276.00 0.20 0.05 0.02 58.00 R int 0.036 0.077 R 1 (I > 2σ(I)) wr 2 (all data) GOF 0.0508 0.1386 1.034 0.0719 0.2038 1.067 observed reflections o. of unique reflections 6291 8037 9694 10347 o. of reflections measured parameters 22640 475 68849 793
upplementary Table 2. Character and second order interaction energies of strongly interacting donor acceptor BOs in norcorrole dimer and porphyrin dimer. The stacking distance was fixed to be 3.0 Å. Donor acceptor BO interactions between a) two stacked norcorroles and b) two stacked porphyrin are shown below. Energy Compound Pair label Donor BO Acceptor BO (kcal mol 1 ) (i) lone pair on C π* C= 6.33 orcorrole (ii) π* C= π* C=C 3.89 dimer (iii) lone pair on C π* C= 3.82 (i) π* C= π* C=C 2.72 Porphyrin (ii) π* C= π* C=C 2.70 dimer (iii) π* C= π* C=C 2.68