Institute of Molecular Physics, Polish Academy of Science, ul. Smoluchowskiego 17, 60-179 Poznań, Poland.
Faculty of Technical Physics, Poznan University of Technology, ul. Piotrowo 3, 60-965 Poznań, Poland.
Molecules. 2019 Feb 14;24(4):688. doi: 10.3390/molecules24040688.
Graphene oxide (GO) was modified by two modified porphyrins (THPP and TCPP) to form GO⁻porphyrin hybrids. Spectroscopic measurements demonstrated the formation of stable supramolecular aggregates when mixing two components in solution. The Fourier transform infrared (FTIR) and Raman scattering measurements confirm π-stacking between hydrophobic regions of GO nanoflakes and porphyrin molecules. On the number and the kind of paramagnetic centers generated in pristine GO samples, which originate from spin anomalies at the edges of aromatic domains within GO nanoflakes. More significant changes in electronic properties have been observed in hybrid materials. This is particularly evident in the drastic increase in the number of unpaired electrons for the THPP-GO sample and the decrease in the number of unpaired electrons for the TCPP-GO. The difference of paramagnetic properties of hybrid materials is a consequence of π-stacking between GO and porphyrin rings. An interesting interplay between modifiers and the surface of GO leads to a significant change in electronic structure and magnetic properties of the designed hybrid materials. Based on the selection of molecular counterpart we can affect the behavior of hybrids upon light irradiation in a different manner, which may be useful for the applications in photovoltaics, optoelectronics, and spintronics.
氧化石墨烯（GO）被两种改性卟啉（THPP 和 TCPP）修饰，形成 GO⁻卟啉杂化物。光谱测量表明，当在溶液中混合两种成分时，会形成稳定的超分子聚集体。傅里叶变换红外（FTIR）和拉曼散射测量证实了 GO 纳米片的疏水区与卟啉分子之间存在π-堆积。在原始 GO 样品中产生的顺磁中心的数量和种类上，这些顺磁中心源于 GO 纳米片中芳香域边缘的自旋异常。在杂化材料中观察到电子性质的更显著变化。对于 THPP-GO 样品，未配对电子的数量急剧增加，而对于 TCPP-GO，未配对电子的数量减少，这一点尤为明显。杂化材料的顺磁性质的差异是 GO 和卟啉环之间π-堆积的结果。修饰剂与 GO 表面之间的有趣相互作用导致设计的杂化材料的电子结构和磁性质发生显著变化。基于分子对应物的选择，我们可以以不同的方式影响光照射下杂化物的行为，这对于在光伏、光电和自旋电子学中的应用可能是有用的。
