The 2D layered organic-based magnet ½FeðTCNEÞðNCMeÞ 2 ½FeCl 4 (TCNE ¼ tetracyanoethylene) exhibits a unique macroscopic magnetic bistability between the field-cooled and zero-field-cooled states, which cannot be explained by either superparamagnetic behavior or spin freezing due to spin glass order. This magnetic bistability is described through consideration of the ensemble of uncoupled 2D Ising layers and their magnetization reversal initiated by a field-induced nucleation of magnetic bubbles in individual layers. The bubble nucleation rate strongly depends on the external field and temperature resulting in anomalous magnetic relaxation. DOI: 10.1103/PhysRevLett.101.197206 PACS numbers: 75.50.Xx, 75.60.Jk, 75.70.Ak, 75.70.Kw Recent years have witnessed growing attention to organic-based magnets due to their new phenomena and opportunities [1]. The magnetic properties of these materials can be tuned to meet the applications, creating ''magnets by design'' [2,3]. This opens a variety of possibilities for developing materials with the desired magnetic properties, such as magnetic coupling, dimensionality, type of spin, anisotropy, coercivity, etc. One of the interesting phenomena in this class of magnets is ''magnetic bistability.'' Notable examples are spin-crossover complexes, which exhibit thermal transition between high-spin and low-spin states [4], high-spin complexes, which demonstrate macroscopic quantum tunneling of magnetization [5,6] and mixed ferro-ferrimagnetic Prussian blue analogs, which display multiple compensation temperatures [7]. In addition, their magnetic bistabilities often can be controlled by the optical excitation [8][9][10][11][12][13].In this Letter, we report unique properties of magnetic bistability of the 2D layered system ½FeðTCNEÞ-ðNCMeÞ 2 ½FeCl 4 (TCNE ¼ tetracyanoethylene) [14]. The dc magnetization displays anomalous irreversibility between zero-field-cooled (ZFC) and field-cooled (FC) states, which we propose to originate from magnetization reversal of single 2D layers through the nucleation and growth of ''bubble domains.'' We show that the rate of bubble generation together with the bubble size and characteristic relaxation time are strongly contingent on the external magnetic field (H) and thermal energy (k B T).Metal-TCNE magnets are a class of organic-based magnets that have been extensively studied. They form a variety of structures ranging from 1-D chain to 3-D network structures, which even show room temperature magnetic ordering for some compositions [15][16][17][18]. For example, the VðTCNEÞx, x $ 2 has a magnetic ordering temperature (T c ) $400 K with highly spin-polarized valence and conduction bands [15,16,19]. Recently, the first crystal structure of a metal-TCNE magnet, ½FeðTCNEÞ-ðNCMeÞ 2 ½FeCl 4 , was reported [14]. The structure consists of undulating layers composed of Fe II ions with a 4 -½TCNE ÁÀ bridging within the layer and two axial MeCNs coordinations [14]. There are no covalent bonds between layers [14]. Additional paramagnetic ½FeCl 4 À anions occ...