Synthesis of Tricyclic Laddersiloxane with Various Ring Sizes (Bat Siloxane)

Abstract

Front Cover: New bat siloxanes fly to the moon: Tricyclic laddersiloxanes with larger side rings are prepared for the first time from Janus rings. The obtained novel, 12‐8‐12‐membered ring laddersiloxane has a rigid silsesquioxane body with flexible oligosiloxane “wings”. Like a real bat, they can move wings freely to apply into host molecules or highfunctional materials. This work is found in article number 2000608 by Masafumi Unno and co‐workers.

13-8-13-Membered Tricyclic Ladder-Type Siloxanes Hybridized with BINOLs: Synthesis, Characterization, and Fluorescence Sensing of Fluorides

“…The Si−O bond lengths of the core T4 ring range from 1.600 to 1.617 Å, while the Si−O bond lengths of the side rings vary from 1.589 to 1.650 Å, consistent with the previously reported tricyclic 8-8-8 laddersiloxane Ph-T 4 D 4 . 9a The Si−O−Si bond angles of compound L1 range from 145.5 to 170.4°(Δ = 24.9°), indicating that this 13-8-13-membered ladder-type siloxane shows greater flexibility compared to the previously reported 6-8-6-membered tricyclic laddersiloxane Ph-T 4 D 2 (Δ = 5.6°), 13 primarily due to its larger side rings. However, it is slightly less flexible than the previously reported 12-8-12-membered bat siloxane (Δ = 29.41°) 13 owing to the presence of two rigid binaphthalenes in the two side rings, which may hinder the free movement of the ladder-type framework to some extent.…”

“…9a The Si−O−Si bond angles of compound L1 range from 145.5 to 170.4°(Δ = 24.9°), indicating that this 13-8-13-membered ladder-type siloxane shows greater flexibility compared to the previously reported 6-8-6-membered tricyclic laddersiloxane Ph-T 4 D 2 (Δ = 5.6°), 13 primarily due to its larger side rings. However, it is slightly less flexible than the previously reported 12-8-12-membered bat siloxane (Δ = 29.41°) 13 owing to the presence of two rigid binaphthalenes in the two side rings, which may hinder the free movement of the ladder-type framework to some extent. The photophysical properties of compounds L1, L2, L3, and L4 were investigated.…”

“…The ladder-type compounds L1−L4 were fully characterized using 1 H, 13 C, 29 Si NMR, high-resolution mass spectra (HRMS), and X-ray crystallographic analysis. The complete functionalization of Si−H groups is demonstrated by the total disappearance of the Si−H resonance (septet, 4.88 ppm).…”

“…1 H NMR (400 MHz, CDCl 3 ) δ 7.88 (d, J = 8.8 Hz, 4H), 7.76 (d, J = 8.0 Hz, 2H), 7.47 (d, J = 9.2 Hz, 2H), 7.41−7.38 (m, 6H), 7.36−7.30 (m, 4H), 7.24−7.19 (m, 10H), 7.15−7.12 (m, 6H), 6.97 (d, J = 8.8 Hz, 2H), 6.76 (t, J = 7.6 Hz, 4H), 6.68 (d, J = 6.8 Hz, 4H), 0.39 (s, 6H), 0.18 (s, 6H), −0.08 (s, 6H), −0.28 (s, 6H). 13 C NMR (101 MHz, CDCl 3 ) δ 150. 53, 150.29, 134.52, 134.47, 134.32, 133.94, 132.38, 131.41, 130.36, 129.79, 129.68, 129.42, 129.00, 128.07, 127.94, 127.76, 127.23, 126.16, 126.12, 125.94, 125.86, 123.74, 123.41, 121.27, 120.81, 77.48, 0. 55, 150.41, 134.95, 134.58, 133.82, 133.46, 133.43, 133.03, 132.15, 131.36, 130.85, 130.73, 130.59, 129.17, 129.07, 129.00, 128.60, 128.02, 127.95, 127.82, 126.27, 126.23, 123.13, 122.06, 122.02, 121.41, 21.38, 1.04, 0.56, 0.04, 0. Characterization data for compound L3: 1 H NMR (500 MHz, Acetone) δ 7.90 (d, J = 9.0 Hz, 2H), 7.72 (s, 2H), 7.65 (s, 2H), 7.54 (d, J = 7.2 Hz, 2H), 7.50 (d, J = 6.5 Hz, 4H), 7.44 (t, J = 7.5 Hz, 2H), 7.36 (d, J = 9.0 Hz, 2H), 7.28 (t, J = 7.5 Hz, 4H), 7.18−7.14 (m, 2H), 7.12 (d, J = 9.0 Hz, 4H), 7.04 (d, J = 9.0 Hz, 2H), 6.99 (t, J = 9.0 Hz, 4H), 6.81−6.75 (m, 8H), 2.80−2.69 (m, 8H), 1.28 (q, J = 7.7 Hz, 12H), 0.50 (s, 6H), 0.23 (s, 6H), 0.03 (s, 6H), −0.22 (s, 6H).…”

“…53, 150.29, 134.52, 134.47, 134.32, 133.94, 132.38, 131.41, 130.36, 129.79, 129.68, 129.42, 129.00, 128.07, 127.94, 127.76, 127.23, 126.16, 126.12, 125.94, 125.86, 123.74, 123.41, 121.27, 120.81, 77.48, 0. 55, 150.41, 134.95, 134.58, 133.82, 133.46, 133.43, 133.03, 132.15, 131.36, 130.85, 130.73, 130.59, 129.17, 129.07, 129.00, 128.60, 128.02, 127.95, 127.82, 126.27, 126.23, 123.13, 122.06, 122.02, 121.41, 21.38, 1.04, 0.56, 0.04, 0. Characterization data for compound L3: 1 H NMR (500 MHz, Acetone) δ 7.90 (d, J = 9.0 Hz, 2H), 7.72 (s, 2H), 7.65 (s, 2H), 7.54 (d, J = 7.2 Hz, 2H), 7.50 (d, J = 6.5 Hz, 4H), 7.44 (t, J = 7.5 Hz, 2H), 7.36 (d, J = 9.0 Hz, 2H), 7.28 (t, J = 7.5 Hz, 4H), 7.18−7.14 (m, 2H), 7.12 (d, J = 9.0 Hz, 4H), 7.04 (d, J = 9.0 Hz, 2H), 6.99 (t, J = 9.0 Hz, 4H), 6.81−6.75 (m, 8H), 2.80−2.69 (m, 8H), 1.28 (q, J = 7.7 Hz, 12H), 0.50 (s, 6H), 0.23 (s, 6H), 0.03 (s, 6H), −0.22 (s, 6H). 13 C NMR (126 MHz, Acetone) δ 150. 63, 150.48, 140.21, 139.87, 134.96, 134.58, 133.74, 133.70, 133.04, 132.14, 131.37, 130.87, 130.66, 130.61, 129.36, 129.27, 128.60, 128.04, 128.02, 127.99, 126.71, 126.55, 126.41, 126.34, 123.13, 122.05, 121.94, 121.31, 15.99, 15. .48, 151.33, 141.69, 141.62, 137.09, 136.77, 134.98, 134.55, 134.46, 132.93, 132.04, 131.45, 130.98, 130.75, 130.70, 130.50, 130.38, 129.76, 129.75, 128.66, 128.04, 127.81, 127.77, 126.99, 126.94, 126.75, 126.63, 126.43, 126.34, 122.96, 122.53, 121.89, 1.10, 0.61, 0.10, 0.02.…”